Process of encapsulation by interfacial polycondensation.

30-06-1981 дата публикации
Номер:
OA0000006163A
Автор:
Принадлежит: Philagro Sa
Контакты:
Номер заявки: 56-00-1978701
Дата заявки: 29-12-1978

[1]

J-V, present invention relates to a method ofF. encapsulating substsheas liquidated visor interfacial polycondensation. Also the capaul3s obtained by this method.

[2]

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 ' iüij piirpiir.se 1 oontsasat ε liquid substance to be encapsulated and a reagent P-DS of the I 'Ir .'V. lAN 'the RasefU, the O ' has8wae wears other immiscible phase the first and - tale.

[3]

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

[4]

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 '? *

[5]

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,

[6]

(.■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 "

[7]

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 the T, oîîouj'oîîouj' ow-to-I©r, avooévcatusllemant a solvent, and the hydrophobic reagent, the O/I-j->- removing yourself-to-arc; this of Be pheco in the aqueous phase containing the réaotiflyKcphilcu - Lo and.rcaots-to-'.' I- has cfono link, in this case, at the same time as the dlfsK 'a-rk0 Cobtc'd, :. cltasêibé of two phenomena has the disadvantage of CoA K'γ■>==. cTAs of * die process; beings too dispersed.

[8]

V<. ' the Xe> ;. e (liov to DTT-iiaKïvénieht, another method is to operate AE F. ;•>•. /.••OD ways the K e épar gold the operation of dispersing the reaction PXR VBE1 - it-said0Autrc; " '- said rats, the d * is dispersed first the organic phase, such as du. - - ii' C'poccOdSija Y-Third chamber, agenda; there>C., V. g at, then adding to the dispersion the réaotif. } ' $<!> . vphn Oj is. *

[9]

With the K ^ RO-STs louç ' RTs known a method of encapsulation by polycondensation the K '■' Koidlo collect kîopolyurô®, (leaked in a first step, to

[10]

•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/'aOüloïithe m transformed, by hydrolysis, a portion of the one or more groups fonotionnelspolyisocyenates into amine functions, these then react readily with the remaining polyisocyenatespolywêao to give this method has an X6 disadvantage of invoking pillowcase reaction (polyisocyanate on the eaïe) slower and therefore request more additional conditions (teaipérature, catalyst) which, complicate its seated in oewre0

[11]

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 *!

[12]

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

[13]

to other confectioneries® ooappositions associating active materials and polymers9 the

[14]

' 9.ï

[15]

compositions produced by this technique have " the advantage of d * use

[16]

9.ï

[17]

much lower amount of polymer, which drives EO veins of waste in 1 ** © treated cultures environment

[18]

L5 interest of these applications requires prior techniques so that improves ©|

[19]

The present invention therefore fear object fc-çrrii * a method which overcomes the disadvantages of these techniques *

[20]

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 ^

[21]

of Be polyfunctional functions contained the earboayle or sulfonyl group,

[22]

th

[23]

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

[24]

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 "

[25]

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:

[26]

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 -...

[27]

Fig. 2: a view El

[28]

the mthe RR

[29]

the locations of other types of1 agglomerated.

[30]

Fig. 3: a view taken perspective of the wall rsgrêsar. figure 2 viewed from within, showing still other types of agglomerates.

[31]

Fig. 4: a perspective view torn cm.>has a type used to make full walls.

[32]

Fig. 5: a perspective view of agglomerate of the•used to make a wall corner.

[33]

Fig. 6: a perspective view of a sinter•c-type used to make 1 - frame D.; opening (windows or doors).

[34]

Fig. 7: a view year perspective of a conglomerate uta_ ΐ. c-c -, ℮ perform 1 * in AC-iremenr. ": c. cverturei

[35]

Figur.-•. e view ρ··;οο;ν: rtive 1' -, tré<

[36]

e-type to produce in particular a wall in

[37]

the m cm as shown in Figure 3.

[38]

Fig. 9: a perspective view of a cake-type ' F uses to perform a feeler as the backboard for bound with floor.

[39]

Fig. 10: each view in perspective of a humped-type 6 used to make a slotted wall for Group:

[40]

with the deck and having a the

[41]

glomêrë F type.

[42]

the c -.: _ij. the L ^ SUI.

[43]

Fig.. 11: perspectiv view

[44]

GM.3 the U '* C.; CFCs {

[45]

h type used to make the angle of a head naked:

[46]

connection with floor.

[47]

Fig. 12•; d is a perspective view: rNs ageIcmérl I used to make each head wall with Ara;

[48]

floor and adapted to a wall in f as shown in Figure 3.

[49]

Fig. 13: a view

[50]

[51]

j-used for real to

[52]

floor -

[53]

Fig. 14: a view

[54]

k type used fear making a T-STS deck and having a length half I type.

[55]

Fig. 15: a view of the EH terspethr L type used to make a lints in Figure 1

[56]

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

[57]

It thus appears that fear reelected uses agglomerates type K ? louse walls, are used type crsb agglomerate for framing open agglomerates used type-b, 1 openings) and type 1 (for the openings); for performing mu agglomerated type e, I#K., D. ; pC-top of a wall, use is made of. hasGM, HR, THE I, J., K..

[58]

In Figure 4, is a represents a conglomerate&type, it is to say the c used for making walls therein

[59]

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

[60]

•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-

[61]

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 *.

[62]

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 -

[63]

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 -

[64]

étlirlfié or relied on, the. polyaorylaadde, the adjuvants are usually added

[65]

"

[66]

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 *

[67]

. / near add-all EEO ingredients to water, the aqueous phase may be before ^ ausemsata HY-I-: - VBE1 Æjêo>Ji in by stirring. The latter is then proBièrô AC phase 'and' AO-to-térivit that the method according to the invention, it is to say to the dispersion for example: by casting of the organic phase in the phaso gi3t? @ I Da are préfjrevioesoncs - vigorous agitation, for example by means of a stirring impeller, to be equalized in the medium droplets # the solution thus obtained is generally acidic, the acidity of the amine salt being a function of the die the salification acidic and basicity of the anûneo

[68]

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 1 moron to 100 miomisoîfes letlet us diesasfeons larger its " possible * but the pines often without advantage supplémentsireI

[69]

The map server in completed Ifeofoiohas this triggers the polycondensation reaction by releasing or CBS ardnespolyfonctioaaelles " by adding lûtiou had - Cm. diverting NLV © based force had equal to that of the hands of the reactant faydrepMle revive functions0Qette base may be either hydroxy&confectioneries "preferably alkali" is a Salt * Large low and strong base® in practice a-j is usilis-a 3 * welded the potassium hydroxide or ammonia® of course " the L>cc.ct should be added if substantial amount deny stoichiometric to the dispersion®

[70]

The GBP PRBSs déolenohsmciit 1b reacting the dispersion is always stirred but nmièr Q more moderate during bare time in "1 to 5 hours viron" to a temperature usually between about 9 °c and the aabiaviec. PSSs TSs péretutosêla ^ / will; the H ion in that theoretically possible * n-© are unintended clan matchmaking as part of the pre ÿfrÿfr.ts a " favorite because they feel undesired reactions and may in some cases of degrading the material encapsulates has

[71]

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 ©

[72]

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

[73]

*

[74]

11 present invention - -,

[75]

1 EEfeple

[76]

Prepared before the justsesyloirsélaagss has " b and following g e Kélange WITH

[77]

300 g of distilled water

[78]

© hydrolyzed polyvinyl acetate to 88 $ if 1.5 mole grams

[79]

silicone oil eatimeusse 8 drops 33 d-® ethylenediamine hydrochlorideO 2 grams of diethylene hydrochloride TR iafidne 30.9 grams

[80]

3 Mixture

[81]

^ I-pp&&sihyl O (? * nitrophënyl) T-&iophosphate (méthylparathlon) xylene resin solution (80 $ active material) 228 grams polyméthylènoplyphényllêliffljp C. 33 grams of isocyanate

[82]

water 100 grams solid pelletized diaiiXlêe 37" 4 grams

[83]

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®

[84]

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®

[85]

After 3 hours of reaction, the microcapsules are filtered and washed to neutral Fïï®

[86]

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

[87]

Residuthe 2

[88]

NC accepted as in the example 1 operates with mixtures has, b and c following mixture has

[89]

400 ml distilled water acetate " 3 PVA® hydrolysis to 88 ^® n mols 1.5 grams oil silicone antifoam " 8 drops of ethylene diamine hydrochloride 43 g of mixture b

[90]

OCOC C.>ivaâthylivaâthyl.c-to-.0 (P-the O nitrophenyl) phosphorothioate in

[91]

the solution tyre tread emic (80 $active material) 164" sebacoyl chloride 5 g to 19.3 gm mixture c

[92]

distilled water 133 grams solid pelletized 32.3 grams

[93]

Obtained capsules's CG is close to preceding whose wall is a linear polyamide (index 2 crosslinker, Ο θ) · Example 3

[94]

Operation is carried out as in example L-dsn3) with mixtures has9 B and 0 the following:

Mixture has

[95]

distilled water

[96]

polyvinyl acetate hydrolysis to 88 c/o mole

[97]

letlet us silicons oil defoamer

[98]

d-hydrochlorideO ethylene diamine

Mixture b.

[99]

OoQo dimethyl-0 (P-0 nitrophenyl) thiophoephate

[100]

zyléniqne in solution ($0 grams active material)

[101]

polymethylene polyphenyl isocyanate

[102]

séhacsyle chloride

Mixture G

[103]

soda into pellets

[104]

distilled water

[105]

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

[106]

Operation is carried out as in the example 1, with the mixtures has)" b and 0 suiUvants:

[107]

Wélange has
distilled water400 rIA
25polyvinyl acetate hydrolysis to 80 $mole1.75 grams
oil - silicone antifoam.8 drops
ethylene diamine hydrochloride21.5 grams
diethylenetriamine hydrochloride mixture b22.9 grams
300.0 dirnétlîyl "=0 (P-I nitrophenyl) phosphorothioate " in solution syiéni that 80 to active material164.5
polymethylene polyphenyl isocyanate7.2 grams
sebacoyl chloride.19.3 grams
Mixture G
35distilled water130 ml
soda into pellets39 grams
OA is obtained capsules g, SD is closethe preceding ones.
the wall of which is a polyamide-urea having a cross-linking of 2.27 g. 5" has biological test
40The remanence is studied biological parathion encapsulated according to

[108]

the prooédé * of the invention compared to the commercial formulation * illustrated in examples 1" 3 and 4 (I ^ C.C. ^)

[109]

400 grams

[110]

1 5 grams

[111]

8 drops 43 grams

[112]

164.5 grams

[113]

7.2 grams 19.3 grams

[114]

32.2 grams 133 grams eoroàatré NC-to-alsiosaable to 4ô0 ee/L of active material.

[115]

The, e sêpsaloa are used as an aqueous suspension in an amount of&YI grams ^ L-SD>material activated *

[116]

The d® /Puitb SU tower oD spray, treated, up in unit ruiss-to-illamants back plsata bean, stage two sheets cotyledonary étalêuj;, the apical bud opràs have destroyed, a suspension or an aveoéüiiilgi: ovrjQ OD; exercice:;; activated to be tested in accordance with a scale of dose expressed I-cents / ΐ· ο 1 AIS' plants treated, taken washers sheets had ' beet(m is the varying tosÿs, either immediately (the JD), or following a number e ->jio3ontjcfenrj OD (JvXO J;4s j-R-I-, j * 15" j + 21, jf30), each washer is placed. - ν - ·;. airôtcîtoobêè: l3, clnïis inserting 5' crawlers, at 3rd stage Iy. jfAro, OD nosiuolle cotton (Spodoptera littoralis littoralis) to control the effie-I agonist. - - * - ii: O-inaaotioids residual of the dobby * each boot Petri then 9.ï ' I-dintjïms cl £5a3O obcaurity in an enclosure at a temperature of 23 °0 *' I- Y)>Y ' liroiiclits after 48 hours a relative, after the miss in oontaot, lo and count tracks effoctrie is dead and live * Table follows" hrtanx gives the formula for each of wrtsiity tested, at a dose of O/50 OD 'd, a CB Uitifes activates, * as a function of time

[117]

11; ka-" rébievd aircraft
e e2 * 53* 100J100jioojioo* 100jioojioojioo
iSjO?; loo' 100ii 70: 50; 4o*!; 40>
i-O2.27100!jioojioojioojlOQjioojioo100 ;
%the IT-::T-OT-:
. ;OT-:T-:T-::
Othe I 100: the Othe O *0 *::::
:OT-T-:::t-:

[118]

H4f&

[119]

c.

[120]

O

[121]

Index of

[122]

Negative electrode: '>iéo

[123]

back ospsrioa

[124]

f - mortality the K~'

[125]

rF

[126]

OJ j. Jfl jj + 2 jj + 4

[127]

J + 8 °3 îj + 15îj + 21:j + 30

[128]

Τ℮ΐ, Λ·ΐ

[129]

Gcaa_. F. ·, Λώ 1

[130]

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.*

[131]

11 ill-C? ER loo ΐ℮ β ΐΰ'd " DOT ILO greatly accelerated rats have shown oral aigVe historical models quo to the 1 ΐ -: - / Α·ύ&ECs of £jclàè to spent ΐ ¾ of about 38 m to ^ ^ ^ ITAC EXC/kg of material, eoit about T Ilya even mentioned a CB fbrnïiîë the business, also expressed in equivalent to JIS I-OD ' vatllvatll.oa pure otherwise. said, the * formula according to the inventio is seven faith-s at least toîdqaa that the reference, when performed *

[132]

Essiïiple6 E teoateoa.j. sulfite ΰΡΐχηinvesticiAs volatile

[133]

The I ℮ο ε ώ is 3 in 1 *" confectioneries with mixtures 1 knew} EI B following C.

[134]

MelanpGCs to

[135]

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

[136]

E ^ emem.oï ' ûiûi.ét'iJÿlWherein Sj: fl. u-? 5t Jifl.! :.l-<; 32ÿoï-to-otMolotMoaatô -!

[137]

(ciaoï-to-Æéphoc.) 170 grams poxviral ^ ^ I-étlÿll-th 1 oyciiata 33.8. gramsKêlsagthe O 0

[138]

soda in pellets 37 * 4 g distilled 100 grams

[139]

JjpïèstAliratien TDC washing, OA is obtains rrâcrooepsules, whose

[140]

the PSS? RO is the O&V.polptivéo having will index reluctant eolation of g8 53I The speed of. 3 004&' of £atîva newly-V. in-:,; than1.!; Lobbyists is " çtaKLeæeatdiffdauêeIΒχ℮τ φο 7, 8 1^Ae 'i-to-stored characteristics-to-letioVi D.5 iM&cffcic&of volatile by polyuria "

[141]

Is © father PK>9.ï, iÆ3 in L9exoi:: CLP 1 with the raslsagosWITHOB}GsuivantsgKélange

[142]

distilled water 433 RIA acetate pelpvinylebydi-to-clyjé to c5 β © Eolss has

[143]

oil silicosis ii®t5 Boo&its

[144]

chloi'chloi' hy-to-dïate D.O £1 ethylene FEDs do

[145]

chloïhydvsbo · ¾ of ethylene tuic-to-two-high

[146]

Mixture b

[147]

S ohloronvéthyl " 4)9 the O âlûttylplKujpiiOAOtMolotMo&ATEs

[148]

(chlOîrSép ' the O?.)

[149]

diisooysnato toluene

[150]

polyméthylèa-s-polyphênyliavoyanato

[151]

Emailangel 0■

[152]

9 * 675^Aqueous soda

[153]

C/O0

[154]

2.00 grams 6 33.2 grams 30 drops " 3 grams

[155]

170 grams 898 grams 25 grams

[156]

99 WITH 38 aIs

[157]

After vatiya screens. and 1 is forvalQ the capsules (the O?) © derrick has "" guesthouse acknowledges to 30 "0 (peeled - / ifelè"), £2 activated material

[158]

Eaoapsulatiea ΒχΘΐκρΐΘ 8, 2^d-SU iîiLioetiei&th volatile Ta-polyaBide-urea "

[159]

Of OA operates ciuüuj in L3e_. 1 ethylene oxide with the ISS ^ "" ôlanges has, b., following 8 0

[160]

distilled water451 ml
polyvinyl acetate hydrolysis to 85 $mole1.75 grams
oil silicone antifoam6 drops
&hydrochlorideO ethylene diarndne21.5 grams
hydrochloride of c&ethylene triamine ml. angel-tooth ohloroséthyl ^ " cUétbylphosphorothiolothionate 0.022.9 grams
(chlormephos)165 grams
sâbaooyle chloride8 9 grams
the isocyanate polyméthylsaepolyphéaylfcîélange 017.6 grams■
fishing 9,875 "73 mi
% of O18 fM

[161]

bitter filtration and washes is formulated the capsules (c8) if in aqueous 30 $3 a-guesthouse (weight/weight) of active material *

[162]

Example 9 **

[163]

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.

[164]

The dead ground is mixed respectively by spraying with mV aqueous suspension enclosed capsules obtained corresponding to example 8 and agitation in the case of granules * mixing is effected such that the dose of material activated is the same in both SAW and/acre * equal to 2 kg

[165]

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 *

[166]

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

[167]

(e* 1OJOJ. ψ 30t-T-J * 45t-L.
|GhlorEiéphosIT-T-
grams encapsulated1THE ICOT-100T-641
* chlorméphôsOthe IT-T-
T-T-T-T-
f. granule1100T-76the I16"
O witness:2:3*2T-
:1T-

[168]

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 coiùm ensuring the mth progressivity in 1g avtiveso materials

[169]

Example 10 grams

[170]

Based on Skuaipîytotosdcitê-treating seeds of blê "

[171]

0a tvrite® by prlvlrisati&^ n-, Eoroagnx of filter paper placed

[172]

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?- y by Lmldifioaiion9 keys grcnulésehiorméphos of business (to 5; e. - P-n-j-LC AIs. OD Kxtiiuoaotiv®} on ISAF filter papers placed has " I-background OD boxes to EB? étrAo the surface filter papers and the amount concentration based on willwill matièra activates applied is calculated to match i'm< end fi® 0S 5 iDA/Ba to its DS full field (processing " ^ baade located by the O

[173]

SEA OD wheat grain are placed onto papers filtreso

[174]

Is to verbs·: ·; ≈ ην lorj Ra of legal Petri with their covers and allowed to remain, gemdnatioa AE produce® to Lthe FF dark and tesipératur © ambisnteo after 3 jeuufcjis nota derivatives look generally shoots with a score range of between 0 to 6 (0 hr phytotoxieity snack9 6 ≈ complete destruction of growth) of O

[175]

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® with C containing fine ohlorméphos exert no® phytotoxieity^8 while the

[176]

the ORC with mental mnlaiioa ^ voiclGgronuléao had

[177]

Example 11 grams

[178]

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 5&C. Pi cAT and shown that the latter has a 50 the EL (léîhdo dosage to 50 w) of ' 12 BgjfKg while the formula encapsulated does in the IFC-to-tess conditions as a EI 50 about 1600 mg/kg in "this example illustrates clear&rasnt the" drop contributed by the considerable forces the DS toxicity provXl® according to iuvvwvirwn rendering the chloraéphos® intrinsically toxic 5 Eanipulablo wide margin with the DS séouritée ' example laoupanlatioa 1g 8 MB of herbicidal suspended in xylene e

[179]

It is performed in the example 1 cjraîv® with the suspension b and concentrated solutions are inherently praise 8 and g

[180]

SsototioaWITH

[181]

© distilled at 400 grams aoétats of-polÿvinyle hydrolyzed to 88 $ th " mole 2 Receive

[182]

8 drops defoamer huilotâlioon®-hydrochloride5 33.2 g of ethylene diamine

[183]

c! I-ethyl-amino such mid® 30.9 gramsSMpïeuipu b.

[184]

100 grams xylêuo

[185]

1 - (Ρο yew■.. phêayl-propyl) - OH-., hence he * dimethylurea (2 to 10 um in)

[186]

100 grams of poly Tp0.7&proiuron ^ ^ jtldàiîQpolypliéayli3Goysaato 33.8 grams§îisp3 ^ ': lo' 9.ï 0

[187]

soda O pads 37 * 4 grams

[188]

water 100 ml

[189]

the lyres filtration and washing, the 379 g of a suspension réoupère

[190]

a CB aqueusoaieroeapsules, titrating 24 * 5 wt. - $Ν (Ρ. isopropylphenyl) -

[191]

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.

[192]

13 Grams Esssngjls encapsulation of a fire retardant solution * xylene resin,

[193]

Oïi accepted as in the example 1 operates with mixtures has, following b and c %

[194]

Kêlaugo has

[195]

© 400 g of water distilled © eét&To of PVA® hydrolysis to 88 $ had 2 grams antifoaming fciliooaa mole fabric 8 drops ohlosiiydïat © di ethylene sorting alder 65.3 g of mixture 3

[196]

xylol 132.2 grams polymétbyllaopolyphénylisoçyanat © 33, 2~3 grams sorting9 3 dibromepropylptosphata 132.2 IMXaage grams G

[197]

133 g of soda water g-I-pelletized 36.9 grams

[198]

/ filtration and washing. near neutral pH, the product dried at 60®eët c in current air® *

[199]

Give a powder to touch the SEO made capsules 2

[200]

to 76 $40 containing by weight ' of flame retardant, the remainder being coirposé traces xylèa © and polyurea constituting the walls of the capsules *

[201]

The PU Εχ℮ 14 sec encapsulating® agent in solution sylenic antioaone xylene resin grams

[202]

It is performed as a non in II for instance I with mixtures has " b and following g %

Hel angel has

[203]

400 ml distilled water polysinyle acetate hydrolysis 88 P into 2 mole grams anti-foaming silicone oil 8 drops hydrochloride diethylene triamine 52" 2 grams Uélange b.

[204]

polyrnéthÿiènopôlyphênylisocyanate 3313 grams 150 g of xylene triphénylphocphine 90 * 1 gm Kélanfe grams

[205]

water 133 grams soda in pellets 29 * 5 grams

[206]

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 W - containing about 50 $ triphenylphosphine, 27 $ of xylene and 23 % of polyurea constituting the walls "



[207]

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.