Process of encapsulation by interfacial polycondensation.
JF et cnoapsrl and ion eubster-SEC liquids by interfacial polycondensation 5 has been long been hatching I-strip 3. The principle of the method involves contacting High ajcond a reagent capable of reacting with the first by giving an in-lycnnd.nv. rt ., the ISEs&d3 upon contacting of the two phases, both conposés 10. rêggiss-to-ii.ut to 1' interfaces ofC phases and, by polycondensation, create a wall ρ ΐ · 0 5: SAQ author DUS drops of liquid substanoes " capsules obtained••* PC-V-I: :•Qtro1 if dried evict to being® used. In the case the bends; F., ; HVV. the pkpk.cc dispsrséo is organic, while the second phase, di-dispersing ssrsvntnUiou OD " sulfo. i.e. the aqueous ** e reaction Mycobacterial EF-15 mmi VI - L-IR. The DIN pupsion tumblers - type " oil in EAA '? * ii poîyuVre constituting the wall of the capsules obtained may be a polryctlfvnarjidQj. a polyester, a polyether, a polyurethane or a polyurea or CAT/cupolrmlrescosprenart at least two types of ester units, ether, (.■V.B Operational) j-UT ' a-eth:; 'la or uu.rsco reagents useful for the formation of polyi .'; - is oopoîyî VC3. ^ LEONARDO AUDITORIUM CI-doysus must be at least di-functional e. The présdo ; - οΰΐΐρο 3 functional R-; at ahead. two causes cross-linking of the oha&nsec-Y olyraériquea also they " Dd.bior-s-perticniiero RODAS and implementation of this general approach have been proposed l® AU involves simultaneous dispersion and reaction -, ;η, η ¾] initially, preparing an organic phase the conprenant. subai-to-pp O With the K ^ RO-STs louç ' RTs known a method of encapsulation by polycondensation •diüj, ... - peppers D'Uij-d-I-1 'AON are, an organic phase containing the substance to be encapeulc - - Receive · .:. ·· ¾ year motorcycles YF polpol.vi ρ ο aaato / - 0, then in a second stage to trigger the/'aOüloïi Cependantj techniques for® encapsulating substances by interfacial polycondensation have finds applications in the Lorraine - the most diverse eoæ® 3O not? for example, inks, dyes, paints, fragrances9 the food products, the prodoits [pharmaoeutic and phytosanitary purposes *! This technique is particularly suited to this last domain,: SROs it provides compositions release the actives (insecticidal} herbicidal, fungicidal © the O) controllably ^ passage through the polymer wall) thereby allowing in particular a reduction of} a reduction in toxicity to handling and on crops © further " by to other confectioneries® ooappositions associating active materials and polymers9 the ' compositions produced by this technique have " the advantage of d * use 9.ï much lower amount of polymer, which drives EO veins of waste in 1 ** © treated cultures environment L5 interest of these applications requires prior techniques so that improves ©| The present invention therefore fear object fc-çrrii * a method which overcomes the disadvantages of these techniques * It relates AU process d9 encapsulating d°ua&liquid hydrophobic substance by polycondensation interfaoiale which comprises, in a first step, dispersing, in an aqueous phase, the organic phase containing tlife hydrophobic substance liquid th encapsulate and healthy at a reactant hydropho ^ of Be polyfunctional functions contained the earboayle or sulfonyl group, then in a step Léger, causing the polycondensation of hydrophobic reagent with at least one amine® polyfonetioanslleoomms hydrophilic reactive, characterized in analgesia in the first step, the aqueous phase contains 1 * anine polyfunctional, the amine functions of which have been rendered unreactive by salification and that, in the second étap ©8 the polycondensation is initiated by releasing the amine functions by adding to the aqueous phase *} D.B an equivalent amount of a hot-force greater than that of the amine " In the sense of the present invention, the term11 material " a compound liquid or solid, substantially hydrophobic, i. e.=substantially insoluble in water and which is inert to the reactants hydrophobic * the case where the male assembly means are in the form of d is the vertical bar I which is locally amino is now describe in detail, as the non-1 alternate embodiments of agglomerates according to the investme referring to Figures which represent: Fig. 1: a perspective view of a wall réails means agglomerates according to the invention showing di types of agglomerated UG ' should be employed for Reso the problem angles,, openings, andc -... Fig. 2: a view El the locations of other types of Fig. 3: a view taken perspective of the wall rsgrêsar. figure 2 viewed from within, showing still other types of agglomerates. Fig. 4: a perspective view torn cm.>has a type used to make full walls. Fig. 5: a perspective view of agglomerate of the•used to make a wall corner. Fig. 6: a perspective view of a sinter•c-type used to make 1 - frame D.; opening (windows or doors). Fig. 7: a view year perspective of a conglomerate uta_ ΐ. c-c -, ℮ perform 1 * in AC-iremenr. ": c. cverturei Figur.-•. e view ρ··;οο;ν: rtive 1' -, tré< e-type to produce in particular a wall in the m cm as shown in Figure 3. Fig. 9: a perspective view of a cake-type ' F uses to perform a feeler as the backboard for bound with floor. Fig. 10: each view in perspective of a humped-type 6 used to make a slotted wall for Group: with the deck and having a the glomêrë F type. the c -.: _ij. the L ^ SUI. Fig.. 11: perspectiv view h type used to make the angle of a head naked: connection with floor. Fig. 12•; d is a perspective view: rNs ageIcmérl I used to make each head wall with Ara; floor and adapted to a wall in f as shown in Figure 3. Fig. 13: a view j-used for real to floor - Fig. 14: a view k type used fear making a T-STS deck and having a length half I type. Fig. 15: a view of the EH terspethr L type used to make a lints in Figure 1 by indicating letter on CLE that 1 the type to which they belong.. I Figures 2 and 3 is provided. Each of will be described by reference to derail in It thus appears that fear reelected uses agglomerates type In Figure 4, is a represents a conglomerate&type, it is to say the c used for making walls therein The agglomerate generally by made the tone of nignonnstta in 20 includes an upper bearing lower 2 3 and two faces D.! bearing LUTs to contact others has froze upper surface are arranged sensu lato (relative to the vertical axis it s therein two male assembly means and £7 an I-beam shape (the vertical bar transversely confectioneries e. the agglomerate)? each means of assembled. respectively substantially centered on sings denial-by the upper bearing face 2 and projects toward the ha inhibitors/f e aiïdïisspolyfonotiowaellee useful as hydrophilic reactive to S; - .,, of the present invention, it may be mentioned in particular amines alipha 'ii' I-·: ΐ - · or aromatic, difunctional as, for example, preferably L9 iCU&éîb./ I-amino ., but also the phenylene diamine, toluenes - diami •born, the IO an HO - - -. jméthylênediaff&does or piperazine as well as amines to more than two 'faith'>. - L .vi * has such as, OD preferably ethylene di-amine sorting, but also the MS (hr. - I-©.<AC*:..>/! - àno) triamine derivative, the - triaminopyrimidine 1.3 " 5 benzene, the triaminopyrimidine~2, 4|6 toluene, eico ^ - I- γ, . ·, ·, · 1 ¾ method embodiment according to the present invention prepared all the dO a U ' -•each of two immiscible phases * the organic phase is obtained by (ïiâlange of the liquid substance to be encapsulated with the reagent hydrophob-in. a-lambda 1 ον ¾ the psopoi ' ing indicated above. This is achieved with dj "the R - 1 nor :! is if the liquid substance is homogeneous (with or without solvent) or dispes 'a-ii.d.on if the liquid substance is further meflte dispersion or suspension · 1. ·· 3 U.S. solvent' organic *. 9.ï-to-lsise aqueous is prepared® by dissolving a water-soluble salt previously '. -. ;. it; obtained silicification of 1 * amine polyfunctional using Ad 1; mineral such as a hydrohalic acid, in particular hydrochloric, an acid? pevhalohydric or organic, especially acetic acid, acid méthanesalfoaiq "2j acid beaaèa® ^ ulfbnic or paratoluene sulfonic acid", this phase aq values-to-'.n;; iTÿ can also ' be supplemented® with anionic, cationic or nonionic customary · interfacial polycondensation processes. ; there PSC-to-aidîSit in many instances, these adjuvants are not required therein - FARs against, 1' aqueseuse adding to the phase of a protective colloid is: ου;ν .,, 1 · · , ?% ' .3®Hou®, fitting it." it is made before or after the dispersion. As colloïcb; " P-voters suitable, include for example polyacrylates, the méthyicellulose, the aiai.cool polyvinyl could be more or less estéri - étlirlfié or relied on, the. polyaorylaadde, the adjuvants are usually added " to OD 0.1 to 5 $rairai.son weight of aqueous-phase 1. If desired, the properties of Cl " LOC colloids may also need to arsiisr agents aniiKOTus % V!. '; 3, in particular those based on silioones * . / near add-all EEO ingredients to water, the aqueous phase may be before ^ ausemsat that 'll fork scene; and for détoninor IC réguiaviser their dimension." The force to * ^ - ^ a7aîst PVst stirring. - 11!; reelected of maaièrô that droplets ai is a size requirement for Cl® about The map server in completed Ifeofoiohas this triggers the polycondensation reaction by releasing or CBS ardnespolyfonctioaaelles " by adding lûtiou had The GBP PRBSs déolenohsmciit 1b reacting the dispersion is always stirred but The above-described method has been shown in intermittent operation8 but it can be adapted to a continuous operation principles example by adjusting the rate of insertion key reagents, of the draw rate of OD eapvulosg - speed for a machine that® the dispersion © Finally the controlled cap-iulcs Gys " vu33 according lo and method are optionally, so as per se of O; N Nhas separated, the aqueous pH vi lavôes then at a substantially neutral pH and dried © it are then ready to be used " is such quellse a-j as DIOP either its? vaion or. aqueous évision " according to the nature and properties of the substance encapsulated © Da Vinci that 1®© rcamplGsrecherchéso applying the following are given as a guide to illustrate 11 present invention - -, 1 EEfeple Prepared before the justsesyloirsélaagss has " b and following g e Kélange WITH 300 g of distilled water © hydrolyzed polyvinyl acetate to 88 silicone oil eatimeusse 8 drops 33 d-® ethylenediamine hydrochlorideO 2 grams of diethylene hydrochloride TR iafidne 30.9 3 Mixture ^ I-pp&&sihyl O (? * nitrophënyl) T-&iophosphate (méthylparathlon) xylene resin solution (80 water 100 grams solid pelletized diaiiXlêe 37" 4 grams A cylindrical reactor. stress during a liter provided with a stirring impeller Shear and an agitator frame carry out agitation more moderate, loading the solution has® In this solution stirred impeller, is poured quickly the organic solution B® after 45 seconds about, the dispersion is satisfactory, the turbine is stopped TDC the testing will proceed under stirring frame® upon shutdown of the turbines, is poured quickly the aqueous soda solution grams® After 3 hours of reaction, the microcapsules are filtered and washed to neutral Fïï® GnRH obtains capsules containing methyl parathion whose * range sizes ranges from 20 to 40 microns and having an index of cross-linking of the polyurêe constituting the wall is 2.53 Residuthe 2 NC accepted as in the example 1 operates with mixtures has, b and c following mixture has 400 ml distilled water acetate " 3 PVA® hydrolysis to 88 ^® n mols 1.5 OCOC C.>ivaâthylivaâthyl.c-to-.0 (P-the O nitrophenyl) phosphorothioate in the solution tyre tread emic (80 $active material) 164" sebacoyl chloride 5 g to 19.3 gm mixture c distilled water 133 grams solid pelletized 32.3 grams Obtained capsules's CG is close to preceding whose wall is a linear polyamide (index 2 crosslinker, Ο θ) · Example 3 Operation is carried out as in example L-dsn3) with mixtures has9 B and 0 the following: distilled water polyvinyl acetate hydrolysis to 88 c/o mole letlet us silicons oil defoamer d-hydrochlorideO ethylene diamine OoQo dimethyl-0 (P-0 nitrophenyl) thiophoephate zyléniqne in solution polymethylene polyphenyl isocyanate séhacsyle chloride soda into pellets distilled water The c ^ capsules is obtained, having dimensions of preceding9 the wall of which is a polyamide having an index of urea crosslink 2I 0îe Example 4 Operation is carried out as in the example 1, with the mixtures has)" b and 0 suiUvants: the prooédé * of the invention compared to the commercial formulation * illustrated in examples 1" 3 and 4 (I ^ C.C. ^) 400 1 5 grams 8 drops 43 grams 164.5 grams 7.2 grams 19.3 grams 32.2 grams 133 grams eoroàatré NC-to-alsiosaable to 4ô0 ee/L of active material. The, e sêpsaloa are used as an aqueous suspension in an amount of&YI grams ^ L-SD>material activated * The d® /Puitb SU tower H4f& c. O Index of Negative electrode: '>iéo back ospsrioa f - mortality rF OJ j. Jfl jj + 2 jj + 4 J + 8 °3 îj + 15îj + 21:j + 30 Τ℮ΐ, Λ·ΐ Gcaa_. F. ·, Λώ 1 the Tb tabljca retracts toto clèir-to-hydraulic circuit status quo, under the conditions of the example, OA is olbib to plain ARs '. gg.t iatatioarehiarquable of remanence (total activity its boiitiibitj-d-a) then quo The formula commercial reference is inactive when lo and SU/Da are traiteBŒatbwdoi.* 11 ill-C? ER loo ΐ℮ β ΐΰ'd " DOT ILO greatly accelerated rats have shown oral aigVe historical models quo to the 1 Essiïiple The I ℮ο ε ώ is 3 in 1 *" confectioneries with mixtures 1 knew} EI B following C. MelanpGCs distilled water. 433 grams acetate - ρ: · ; · 1.! J. K./ loLINEAGE lvA EE to 85^UG "533.63 2 grams oil silitoj degraded ufeus is 8 drops" hloiah ATEs^43 ethylene copolymers of £λ · ·η. 1 κ 33.2 grams cîûaïhyd 9' ratî of uiétli/Isoleucine1.3 YI tïieaiae 30" 9 grams Stélan3 pGCs E ^ emem.oï ' ûiûi.ét'iJÿl (ciaoï-to-Æéphoc.) 170 grams poxviral ^ ^ I-étlÿll-th 1 oyciiata 33.8. soda in pellets 37 * 4 g distilled 100 grams JjpïèstAliratien TDC washing, OA is obtains rrâcrooepsules, whose the PSS? RO is distilled water 433 RIA acetate pelpvinylebydi-to-clyjé to c5 β © Eolss has oil silicosis ii®t5 Boo&its chloi'chloi' hy-to-dïate D.O £1 ethylene FEDs do chloïhydvsbo · ¾ of ethylene tuic-to-two-high Mixture b S ohloronvéthyl " 4)9 the O âlûttylplKujpiiOAOtMolotMo&ATEs (chlOîrSép ' the O?.) diisooysnato toluene polyméthylèa-s-polyphênyliavoyanato Emailangel 9 * 675^Aqueous soda C/O0 2.00 grams 170 99 After vatiya screens. and 1 is forvalQ the capsules (the O?) © derrick has "" guesthouse acknowledges to 30 "0 (peeled - / ifelè"), £2 activated material Eaoapsulatiea ΒχΘΐκρΐΘ 8, 2^d-SU iîiLioetiei&th volatile Ta-polyaBide-urea " Of OA operates ciuüuj in L3e_. 1 ethylene oxide with the ISS ^ "" ôlanges has, b., following 8 0 bitter filtration and washes is formulated the capsules (c8) if in aqueous 30 $3 a-guesthouse (weight/weight) of active material * Example 9 ** The remanence is studied biological chlormephos microencapsulated according lo and process as shown at 1 * exemple 8 in comparison with the formula cornu cells thank you have made, perceived a granulate to 5 $by weight of active material. The dead ground is mixed respectively by spraying with This mixture introduced into a saucepan sulfo " with the earth's surface thus treated is deposited through cup *, 50 * 4 days old larvae, fly (Eases scrofa domestica) O in each test object of two repetitions * A Ga inaugurating then respectively immediately (OJ) and after•of 30 (Jv3û) and 45 (j + 45) jovrs a monitoring of the number of dead larvae in compared with its as controls those deposited on the surface of the earth deposited © in pots, but not previously treated with chlormephos * in monosaccharide condition observed the mortality rates following 1 This example clearly shows the ore ehiorméphos encapsulated by the method of the invention has MWI insecticidal activity AOAs only immediate9 as good as<Morffllphos in granules but also more persistent ©9 have " O indispensable ESAW known Example 10 grams Based on Skuaipîytotosdcitê-treating seeds of blê " 0a tvrite® by prlvlrisati&^ n-, Eoroagnx of filter paper placed at the bottom a CB to GOL T-e-j of Ktrij to IO 0 sD IDA®& 5 if iure of dispersing a concentrate éisfil OD! "! abl3 of ecpselGachlormephos obtained based on example 1 * V-dare UG in parallel? SEA OD wheat grain are placed onto papers filtreso Is Dsîïs conditions therefor is obii vancomycin-resistant enterococcus agent © qus® at the dose of 10 kg/ha in the capsules shoots are completely destroyed® to the fissy dosage die active material® the ORC with mental mnlaiioa ^ voiclGgronuléao had Example 11 grams lias seasonally flooded impoundments of oral toxicity aigfôe on white rats with the strain of OPA i0ps dûor&peuléêpboa CAD ^ by the method described in the example 8 and with the bhlorEéphos toto ooiair roicl/(g&misses It is performed in the example 1 cjraîv® with the suspension b and concentrated solutions are inherently praise 8 and g Ssototioa © distilled at 400 grams aoétats of-polÿvinyle hydrolyzed to 88 8 drops defoamer huilotâlioon®-hydrochloride5 33.2 g of ethylene diamine c! I-ethyl-amino such mid® 30.9 100 grams xylêuo 1 - (Ρο yew■.. phêayl-propyl) - OH-., hence he * dimethylurea (2 to 10 um in) 100 grams of poly Tp0.7&proiuron ^ ^ jtldàiîQpolypliéayli3Goysaato 33.8 grams§îisp3 ^ ': lo' 9.ï 0 soda O pads 37 * 4 grams water 100 ml the lyres filtration and washing, the 379 g of a suspension réoupère a CB aqueusoaieroeapsules, titrating 24 * 5 wt. - $Ν (Ρ. isopropylphenyl) - T-the K, the I */ ctlibldyl angers (iooproturon) e the wall is polyurea microcapsules, the diameters are between 2 and 140 willwill morons * release rate in IO © at of 1 * herbicide is significantly reduced. 13 Grams Esssngjls encapsulation of a fire retardant solution * xylene resin, Oïi accepted as in the example 1 operates with mixtures has, following b and c Kêlaugo has © 400 g of water distilled © eét&To of PVA® hydrolysis to 88 xylol 132.2 grams polymétbyllaopolyphénylisoçyanat © 33, 2~3 grams sorting9 3 dibromepropylptosphata 132.2 IMXaage grams 133 g of soda water g-I-pelletized 36.9 grams / filtration and washing. near neutral pH, the product dried at 60®eët c in current air® * Give a powder to touch the SEO made capsules 2 to 76 $40 containing by weight ' of flame retardant, the remainder being coirposé traces xylèa © and polyurea constituting the walls of the capsules * The PU Εχ℮ 14 sec encapsulating® agent in solution sylenic antioaone xylene resin grams It is performed as a non in II for instance I with mixtures has " b and following g 400 ml distilled water polysinyle acetate hydrolysis 88 P into 2 mole polyrnéthÿiènopôlyphênylisocyanate 3313 water 133 After filtration and washing with neutral pH8 the product is dried at 60 °c under current D.O the air0 Give a powder consisting of dry feel microcapsules of 2 to 25 The process for the encapsulation of a liquid hydrophobic substance involves, in a first stage, dispersing an organic phase containing the liquid hydrophobic substance to be encapsulated and at least one polyfunctional hydrophobic monomer having functional groups containing the carbonyl or sulphonyl group, in an aqueous phase containing a polyfunctional amine in which the amine functions have been rendered inactive by salification, and subsequently starting polycondensation by liberating the amine functions through the addition, to the aqueous phase, of an equivalent amount of a base which is stronger than the amine. The process has application to the preparation of compounds which can be used especially in the field of plant health. 1) Method has' substance encapsulation by interfacial polycondensation hydrophoceliouide which consists, in a first step? dispersing, in an aqueous phase, an organic phase containing the hydrophobic substance liquid encapsulating a hydrophobic reagent and at dibs polyfonctionnel functional group containing carbonyl, sulfonyl or then in a second stage, to cause polycondensation of the hydrophobic - reactive with at least one amine polyfonotionnelie as hydrophilic reactive, characterized in that: in a first step, the aqueous phase contains the amine polyfonetiennelie, which tees amine functions have been rendered unreactive by salification and that in the second step, the polycondensation is initiated by releasing the amine functions, by adding to the aqueous phase of an equivalent amount of a base force greater than that of the amine. 2) the hydrophobic substance pure liquid is an organic compound, an organic solution, or a dispersion or slurry in an organic solvent. 3) the reagent - hydrophobic is a polyfunctional acid chloride, preferably a chloride of a diacid and particularly a chloride of a aiacide aliphatic containing 2 to 36 carbon atoms " 4) The hydrophobic reagent can also be a linear a diacid chloride. 5) Preferred hydrophobic reagents are as follows: - the chch.lo.rure sebacoyl, - an aromatic diacid chloride, - a polyfunctional isocyanate, - a diisocyanate, - a trijsoeyanate. " 6) According to paragraph 5, for the case of an isocyanate, using two distinct polyisceyanates as hydrophobic reactants. 7) Are simultaneously used as hydrophobic reactants at least one acid chloride polyfomationne 1 and at least one P-isoeyanateolyfonetionne1. 8J the hydrophilic reagent is a diamine or triamine " 9) Distinct polyfcnctionnelies two amines used as hydrophilic reactive " 10) Are used in particular as hydrophilic reactive aliphatic amine " 11) The amine functions of the hydrophilic monomer have been rendered unreactive by salification with a strong acid, especially a halohydriaue acid. 12) The amine functions have been rendered unreactive by salification with an acid chlohydric. 13) The polycondensation been established in those markets is triggered by addition of an inorganic base " 14) The hydrophobic substance liquid comprises a phytosanitary active ingredient, preferably an insecticide such as methyl ethyl parathion or chlormephos. 15 J of the active material. phytosanitary can also be a herbicide, such as isoproturon. 16) Encapsulated liquid hydrophobic substance obtained by the process according to a, paragraph 3 of the 15. 17) Composition of a substance according to paragraph 16 characterized in that the encapsulated substance is a phytosanitary active ingredient.Mixture has
Mixture b.
Mixture G
distilled water 400 rIA 25 polyvinyl acetate hydrolysis to 80 $mole 1.75 grams oil - silicone antifoam. 8 drops ethylene diamine hydrochloride 21.5 grams diethylenetriamine hydrochloride mixture b 22.9 grams 30 0.0 dirnétlîyl "=0 (P-I nitrophenyl) phosphorothioate 164.5 polymethylene polyphenyl isocyanate 7.2 grams sebacoyl chloride. 19.3 Mixture G 35 distilled water 130 ml soda into pellets 39 grams OA is obtained capsules g, SD is close the preceding ones. the wall of which is a polyamide-urea having a cross-linking of 2.27 g. 5" has biological test 40 The remanence is studied biological parathion encapsulated according to e e 2 * 53 * 100 J100 jioo jioo * 100 jioo jioo jioo SjO? ; loo ' 100 ii 70 : 50 ; 4o *! ; 40 > 2.27 100! jioo jioo jioo jlOQ jioo jioo 100 ; the I : : T- O T- : . ; O : T- : T- : : O : the O the O * 0 * : : : : : O T- • T- : : : t-: distilled water 451 ml polyvinyl acetate hydrolysis to 85 $mole 1.75 grams oil silicone antifoam &hydrochlorideO ethylene diarndne 21.5 grams hydrochloride of cðylene triamine ml. angel-tooth ohloroséthyl ^ " cUétbylphosphorothiolothionate 0.0 22.9 grams (chlormephos) 165 grams sâbaooyle chloride 8 9 grams the isocyanate polyméthylsaepolyphéaylfcîélange 0 17.6 grams■ fishing 9,875 " 73 mi % of O 18 fM (e * 1 OJ O J. ψ 30 t-T- J * 45 t-L. |GhlorEiéphos • I T- 1 THE ICO 100 T- 64 1 * chlorméphôs O T- T- T- f. granule 1 100 76 16 " O witness : 2 : 3 * 2 T- : 1 T- Hel angel has