HUE030320T2 - Oxo-alkohol alapú asszociatív monomer, ezt a monomert tartalmazó akril polimer, a polimer alkalmazása sûrítõként vizes készítményben, a kapott készítmény - Google Patents

Description

ASSOCIATIVE MONOMER RASER ON OXO ALCOHOLS, ACRYLIC POLYMER CONTAINING THIS MONOMER, OSE OF SAID POLYMER AS THICKENER 1\ VN SQI EOI \ EORMt I A DON, AMI FORM! I \HO\

OB I AI NE D TSf^iss^l·' MvérM««: eetsoema new HASBdyge rheology modi Ilers, the .associative monoims of which ts torn ivrothted bt a hvdrophobse gtoop stub o\o Neohols base Implemented in fbimulatiotis comawmg water such -as aqueous paints, these products lead to a phebös«iholofaoétèaaed vkcoshs over a wide range otNhearmg;gt'adicnts, aqi: mosti palhlulidly fhrlhigh .grldifehhn they .'therefcetf#'Pfa^cf|Yf thickeners, ant! p< such cm* a t, a > new taute t f piodmw ,vj q no e hKtry -d p «r" ourm ! „'etwdiuo ne«<> \ mamsu ?\. e no ',\erc>\ v hen ottos. aec» > > au au <, ms formulation, can develop rheological profiles which ate tar more Newtonian than their HASB-type predecessors, and at the same type keep an economically advantageous level: of effectiveness. Such a result is obtained through the implementation of the ahoveme.ntio.ned particular associative monomers. This property is even exacerbated irt a preferential variant which consists in adjusti ng withm a certain interval the dose of chain mown t agent implement, d m the moth M ot mannt tette e of the" s&amp;ti polydieii.

The associative möhöínets functional; aed hy oxo alcohols base hsdrophohte groups cnosMute one object of the : present invention. The Sxtme applies to the HASE-type polymers nvernomimg such monomers, and to then- method of ,-y v,bests. The use of the latter aa thickeners in aqueous ibpsplaiqnspand the respiting fonnulauons, consütuRrÉsii.: final two objects of the present invention.

Controlling the rheology of a paint, both in the stage of its manufacture, and during its transport, storage or implementation, remains a priority at the, current tune. The wide variety of constraints nhaened in each >ri these steps o hues to ,-, mtthqdu tty ,«t dtiViesP flioligiMl ÍÉíévíouts. Nevertheless, it is possible to of the skilled man in the art m ebt strung on circa of the thtckemng of the said paint, both lot reasons of stability over ome. ansi for a possible ..ippheation to a vertical surface, lack of spattenug ,y use moment of unpianenutiou, o- ot sagging suhsequenly, etc. For tins reason the product's which contribute to Ibii rcgphdtpg hco« designated by the terat th-teksners

MitöÄ% :áMfe pi' tnd products hove beess useidÄÄ" lire eesentbd ghPdf^Mies §*$*£ |||$β ipoleçalar weight- Howev^ ...tí^pt:- compounds lsévé a number et' ils xadvas st «ges. such es thon instability eves' tune (see document US 4 673 518k the need te use a large quantity oí them (sec document EFG 350 943 Al), and thcir production costs. notably in term« of wastdtfêabn«:fàé# :feeum^iöÍi::4:3i4©Gi|

Thickeners called Leódat s ce" thickener!·; WW® then created: these are water-soluble polymers haying insoluble hydrophob® gpotspse Such .macromolecales -have an associating character; when introduced into water, the hydrophobic gmnsps tend to assemble in the form of micellar aggregates. Those aggregates are linked together hy the hydrophilic parts of the polymers: a Ö«|^3^e«sicmailaelwiÄ· is then €m*mä wiich causes she sisvoatiy of the medium so he increased. The operating sneehams.m and (hesr ch.naetensfics as aow oeb known und desorbed, tot example ut the documents "Rheology modifiers for wMer-horne paints” finffepp fngfinp Australia. 191:5, pp P-oh and ' Rheologic al modifiers rhr water-based parais the most flexible tools for your formulations'’ Uiuroeoat 97, UATCM, vot. :l:,:;|pA23-442.h

Among these associative thickeners, a distinction is ma|s:: the category of HE HRs iHydrophobically ns eel died Ethylene oxide iJRethane), and II AS Es (ilydrophohsoally modified Alkali-Soluble Emulsions and thickeners). The first relate to polymers resulting from the synthesis between a compound of the polyalkylene glycol Type, m pplytsofyapale, and a« alkyl and/or aryl associative monomer eonsisfing of a hydrophobic terminal gt'{}J.tp. The second relate to polymers of (meih)aeryhc acid, of an ester of these acids and of an associative monomer consisting of an oxyalkylated chain terminated by a hydrophobic group,

TiRURs are the cause of numerous properties in aqueous paints, notably depending on the nature t>l their associative monomer. It w possible to cite the following patent applications registered by the company ΟΟΛΊ EX;H EP Pis39 595 AL which proposes hydrophobe groups haxsng a >o *o carbon atoms so increase die Brookfield*** viseoMtv 01s 1028η8 Λi nhwb devcrihox the use of ptiaywiyivlphenois w nh more than Ίο #ms to i»CK»s»wlpïever Ilié É^íiióg grntef, and finally HP ! 4|S J3S; AH which reveals «tu associative nvnoutei «tOOMstmg<n »K ,u\d msnvsbhouof omthimg an excellent pigmentary compatibility and a high viscosity with low and medium shearing gradient -o ne obtained, fko same ippbes to H. Vst"·- pnajuets hu a inch one e ei notably, mention the i-.dlowing patent applications registered by COATEX™· HP 0 57? 526 As, wind· describes a fatty chain whh linear or branched units of the alkyl and/or aryl type, having 2-6 to 30 carbon atiiiS; to dtnmlpp high viscosities under a lost?; .shearing graÄhf and I V V “"8 \ .., w lm b >kserdns a hi a u bed teámnál chain eompU'Uog to to 24 v at on atoms, to improve the pigmentary compatibility, and increase the viscosity generally, ill the field of the rheology of paints. ahlmogb it: is advantageous to hevpAisew lui ally of pÄPots enabling the xieeosity to be lucre isod over a wide range of shearing gradients, it is also: very useful to have thickeners which will induce a particular rheological profite, depending mi the „whedek «a speed'n -nPuts of the upphcaior or et the format Urn \Wh this t egonk one often reads that gloss and satin paints me advantage-mod) suited m a ’‘Newtonian** prpille, with ||e Mter altooing of their spípnÉhg end a reduction of projections during their application. A "Newtonian” pnkile sigmfkw menretieahx that the msemotY remains unk pendent oi ibe shvaamg gradtom such ptopeUies ,ve m mm s b'e m teat *s \ -¾ ,ct sc, 1 , \> -.si man in the art associates such a profile wob u box degree of vbangt ot x iw<>"hy vk pending ou du shem mg " ue (theogram proportionate s' flatten, m <, o útra-a to ,¾ ps,. ode plastic profile, characterised by a marked fall in the viscosity depending on this gradient ifheogratn prepmttomudv mote tdupmg) In tangible tenus, the lower the raise between the Brook held viscosity at id revolutions per minute, m mPa.s, and the cone-plan viaeostiy, known as the 5,ICT (which corresponds approximately to a speed gradient ot 10,000 0, the closer one comes to a Ncwionmn bchavionr.

Having smd this, puwioed the on <- nain, a ted abuse w seduced, u is, desirable not to lost ntekemng ettk a-, a, r h?g ecivgu?, 'Jus consott λ a w\ cgnuawm wkw'

soa\ bi' rcikvted by ,i som eh ín a soneemotaftt manier for as htph aa possible an ICI viscosity.

Cmremly, Ihe technology oll-IEURs and thaï of H AS Es enables assoaintiw thn.kencra to |N|if0OTtiîai^d. which develop Nexuonùm proxies when they are introduced into aqueous ilpmilaiinns. This is described notably U\ the document ^Disperse phase - thickeners interactions and their mb non ce on Newtonian to non-Newtonian tlow behavior" (Polymeric Matériáig 1995), 73,. 1:9¾).

Its tbc ease of BEURs. reference may be made to the document US 5 500 475, describing a thicken no m tins categon ohmic once unolemented sti an aqueous earn), develops ,* Newtonján pswíüe whilst leading to a dry fdm with a high degree of brightness, w hielt is water-resistanf bird:abrasion^resistMl) and also ÄMlÄ-iiÄPiiÄniöÄßt I iuwevej the IIR'Rn ate *.hemwat sperr es winch me not very solvent in water, und must be put into anionon in the presence of solvents or anrfactants. if their % df aettve material exceeds approximately 25%. and provided they develop Newtonian profiles. This problem U explained in document FP 0 bBd 994 AÍWtld proposed solution is: based: trivially on the use of surfactants, in addition, it will be noted that thiefedtrerd of tho BBBR type, which arc highly concent ruled and contain surfactants, had been sold % the company COAT EX under the names DOAPDR5^ 5da5 and ('NAPÚRA b050, before tU ptiosuy date of this application, md n<nn DATmii the ease of the tirai of these.

And the inipleméhfatiÖP: of solvents ind surfactants to forrmdate the UEllll-dype thickener poses a number of problems. Firstly it will be recalled that solvents arc subject to increasingly Draconian legislation·-.aimed at restricting and evett prohibiting their use in paints. As fot the surfactants of the thickening formulation. dretr nature w such that they destiththse parrds, through mies action wtth the othei surfactants contained to these paints. Consequently, the formulation ofliBURs of Newtonian type in water is only possible provided the polyurethane concentration is drastically restricted (of the order of 20% by weight), which makes these thickeners ineffective.

Among HASIN, the only om \ winch poo e geonmdy erieetne m developing NcvOmuan profiles are thickeners the associative mpnom^ §f wbi|I|: contains mhoxylated olUylphcnols (AiHfsMdhé Inghsb acronym). Au illustration of thorn is to be found in document F P 0 5b0 Ί 14 Al. which louche the use of ethosylatod nunylphonok for the synthesis of the associative monomer of.a HASE-type thickener* sod shows that the resdtmg poHmer enrôles Vo to too rheulog.eal pmdos M bo dciehmed *>ue inhidtieed pm m aspeous patai. Nonetheless, tdkvlphemds am currently widely suspected of being carcinogenic, and dangerous tor reproddatíé'áF'ái'ötóugh -àtil :to!eæàteâP irt the paints industry they nonetheless remain ht the tiring line of the. legislative liâh tuiaps ip this: ¾ '1 he Applicant, however, hiss succeeded in developing new associative monomers, able to be used to the compositum of HASI polymers, giving the skilled man tn the art the following advantages: - the po-siNhw ot dv^eh'ptuy,, w, the nas„s .0 these mw assoemow monomers, i new iat|g0M.MiiSI4>^Ädkcjim,:ihfeAtf'thidiÄhg-'Äit|;dÄ« formuládonover a very lat^e Aheartsrg gradient: interval (and notably over the range of the high gradients), thus avendmg the oo. of RPNRs whxh require solvents and/or surfactants hi their ibmndaiion in order to he effective: - mortVYc;, the.w ate tlucU tiers erahtc pansu dark ;e eked New toman psoftles to he developed, notably tit terms of ratio f Brookfield viscosity at 10 revohtimns per nmtute, in mPa.s. ICI viscosity)« whilst, maintaining a signifiant 1(.1 viscosity; ' lastly, this latter property is exacerbated according to a particular variant of the invention, which consists m adjusting the chain tramf%: WiSAW^it in the course of the manufacture of these thickeners. live said, ducke vem com or an associative asonemer m fonoda t h Ähre:

V m and n are integers of less than 15i\ at least one of which is nom aero. ~ A .mb H designok alkvl groups which ate dt lieront une hem mother, m.J uontg 2 to î cas tvs. atoms, where gump lu gwdateot,*d\ cosignâtes ethylene oxide, and group PC) preferentially designates propylene oxide, * It ddsipites a p^ÄÄÄ»i»itci'pd^, prelerendshy metitaers late. * UUCIV P' f·, chUMCtvfVed 55' that U OUWS-,Us OÎ fît ICUh mie gfOUp Of tCSmulu (Il):

wtee pÄd q deifgpuie integers at least one of which is non-xero, with. S 13, r is uo integer between 0 and 5, preferentially equal tvs 0,

One of the ke\s oi the present invention, (s based on the choice ot coropounds of formula Oh. as a terminal hydrophobic group of the associative monomer of formula (1). This iaUer is traditionally manufactured by ethoxs lation of an alcohol, followed hf functionalization with a view to making it poiymerùrahle. ht the context of the present invention, the Applicant has observed ; that the particular choice of an oxo prohpf adón ed the wntlumanew usso». »me muromots of formel*» <h, nhnh uituratcH go e all th\ props:;ties listed above fo must a till) of these oxo alcohols ts as follows:

where tn q and r have the previously indicated meanings» These are well-known compounds, obtained very simply by hulrofonnylation of an alkene by means of a synthetic gas wtth an il y CO ratio dose to .1. This reaction enables the alkene to he nwnsfonned into aldehyde, which that must only he hydrogenated: in order for Pe alcohol to he able to he obtained. An illustration of this is found itt document WO 2007/066036. Commercial examples of these alcohols are the products sold by the company 6 \0OlÏM under the trade name U,tlm, RdohcnrM, Ai diem * ^ and Sato OR or by the company BAIF™ under the trade name Lutensoi™,

The fact of indicating that the terminal group 11' of the monomer of formula (1} consists of at least one group of formula (0} - and not that it consists exclusively of this group - is related to the lad thai-the khtiaf oxo alcohol results'from the hydroformylation reaction onmnmed ohne, whnh urn also Vad to du formátum ni Imem VcuhoR in addition, m Uns formula, the value indicated for p ; q is the one relative to the majority specie, since commercial oxo alcohols are generally blends or fractions,

Al&amp;ough these ÄiÄ 1¾¾ been used in the field of detergergs (see bdebbiidlsilP 1 ..2PI ti?;Mid US 4 2H0 *H9h they have not yet been inqfiensMfiM IfiriÄ: synthesis of an associative monomer. finally, oxo alcohols are well-known kw having a high degree of loodsgmdabdds cee die aboi ememioned document i s 4 die fiUfi, which common.-; one of the benetlts of the present invention.

Thus a first object of the invention consists of a monormn of tonnula 0);

where; .. m and ,, *e n,ege< ' so less nan 150, at Tao > no o olnU's tan con; a A and B de\ignale aikvl groans which are different rare írom another, ami Kar ing 2 to 4 carbon atoiv.v obere group hr.) ptv teremt ally do,n anales cficvh.ne oxnle, and gtoop 1H* prüfe,emudlv desnw.des prom lene osai, ,- R designates a polymen/able unsamrated group. preferentially methacrylate, whom R' o ehamcteriaeo nr that a commis of ni least one grouping of fivnoul r ill);

v-inue p and g de-agnate unegess at least one of which ts non-aero. w ah 5 p ! go i fi r o an interns between 0 and 5, profeicottalK ognal to 0

Preferentially. this monomer is characterized: inÄhai -¾ BCT designates;the ethylene ovule and m mhem,son '0 and 40. A -uvond ehgvt of tlv pr osera invention ton.-usw of a HAS! -type po| voter corns g. ; og at oi Anahlaeryik: acid, b) oi at least one ester oftvoeth)acr>he acid, u or at itvist ore n odora- ο? fi f ainununinun. < hamulatj)

The Applicant stipulates that the manufacture oi these copolymers Is very well-known to the Ail led man m tbc ait, oho can ietes to the much mg of the documents cited above as the technological background of the present invention. Concerning the influence of the ipanthy οι'chain tnunde? agent tmpiememed in tlie syathcÄbf ÖÄ|:ÄÄ'ife:ili*hl'' pan ultin coenvo Po»,o,\ w ov me seta \p no anno ail -,: a**te -o an an go en no 'This pplpaerp also ch^seMiedip their it eonsisiy e^itreppl ss *v>o by WÉIÉ: altiéit of iis mmmm®. *» d ' rS ss ρηηκίΜ i \ k '*«, » outiï x\K cm b) of 4,V\, to \>! pteiootmahv as η o* <d lojga one ester ηί ϊΠΚ'Οοην,χ',Οο acid, e> iif 2% to difi. preferentially 3% to ISP, of at least one monomer of the afeovememioued formula tlb

In a pro&amp;roPM vanantx this polymer is characterized in that, for Olp ptoppppp of formula (i)> n ~ 0, EG designates the ethylene oxide, and m is between 20 and 40, \ time: ohmét of the presen 1 imenfton eonsvsts of a method lor nvmafaeoae of a IIAbf-t>pe poivnier, through contact m a teaenve medium between &amp;) (medfiacrylle acid, bt at least one ester of tmethiaorylie acid, c ) at least one monomét with the tj^jpôçtuï with pocsibk introduction in the reactive medium, before and/oït.âarisgj'ïÂèyi'aâer the contact bPweenlhe tPmîtituents at, b>

In a |nefercnh-d mmwtî, the said method ts ehamaen/eh m that the (ranker agent ts implemented and in that its mass introduced into the reactive medium ts between i .fob ppm and 4,boo ppm u-laotc to the total vi eight of constituents a), b> and el 1« a completely unexpected manner,, the Newtonian nature of the rheologic,, profile caused bv the pohox'r m the w,nei ss onpuwed nhue n„entammg a smb-naniml thickening of fie a' , a ugh bn e< *g s-λ en in λ pw >v oeuf mum n the no mod \ , KeaeU ? mod m that, lot die monomu of fwmnia (il, n d, ΓΟ designates tin- Ufnlene exnie, tad m o between 20 tani 4h

Ilii msük is epnmtöf pperif íhfteálol 'M$% dtmdbdloh ö| ft eha© rmnsfer agent will in al! ;eu.%ej. mduee thickening ei&amp;nvy ofxlm polymer (sec notably gage: 7 oCnoegmenl EF 0 0BS36 Ai), Mete precisely, h known that an excess of hPosier agent (át leáll ®.b% * IjCM pptn - by weighs relative to the total weight of the engaged monomer# lends io an kpprn#hmRf Φ§ Hs^Älh' PPÎlte ftst£* concomitantly, to a loss of ihiekenhrg ppwgf agroas ffmemim ragjp ni C^hiMng 1ASË Rheology through Polymer Design". iC'E Egsedykv vpi 2, ;»* i, April 2®S, pp. :43-433}.

This*· speihod is also ckEmeteázed in that tie reactive mcdlom cPnsistg: of water w&amp; another organic solvent, preferentially consisting only of water.

This method is also characterized in that the chain transfer apnf Is dimers from among N-dodecvl mercaptan, N~dee>l mfeaplarg octyl naerespfeií, l,k-áln?freapto-3i6-dioxaodtane gDMPC), rf ( 'AS: IdhyAATwf, tllplacic-ftctd, A fourth object of the posent ihygstiog ctMÄAlh Ä nie öf a BASl-ívpe polymer ás; explained previously, as a flpcgAiug ftpnt in an aqueous formnlatipm A fIÉf| agi End fhjcct M the tweseht: Invention consists of art aqueous fomipiatlon containing a HASE-type polymer set explained previously. Including at least One aqueous p.um formulation.

Emmpie I

This tes? illustrâtes ti» use of associative thickeners nseordipg to the prior an (HÄSE) and uncording to hie oneotmn. o rh a ven v tb whs" mug an aqueous gd

Far each ut thé tests n° ! to 6, a fixed mass equal to 10.7 grams of the thickener irr vesting, tuistip wt|| approximate ! gram of a neutralising solution of ammonium hydroxide at 28%. is imraduced otio 215 gmm&amp; of an aqueous solution consistai of 40 grams of deionised water and 175 grams of an acrylic binder Neocryl XK 90 sold by the ddtipuy PSW. imaLi Ί n'ts test illustrates the prior art and uses a d \Sh t>pc assewative dnehcncf mid Ik the company COAIE.\w under the name RheOedfm 5100. Tho thickener ennuies aikylphonoh. IMif.2

This tes? illustrates the prior art. and uses a IMSEmype associative thidmner sold by the company ROHM «&amp; HAAS™ undet the name Acr>soîmHM5 '[yyu).:..e

This teO illustrates the mvendon and uses a HASE-tvpe associative thickener according to the invention, which is apoipÄAbnsistibg, by % by weight of eadi of tts monomers, oi a) 35.5% nt methaerybe acid. b) 52.52 <> of dhyl acrylate, e) I2J% of a ni«tper of formula Up lit which:

•S - '0. ? rd deog.v ν'- , ,mk a .h, «v f e.-uw tes *1 s r vthaeryiaw woup R designates the group of formula (U) where p t g ~ H), r 0- 1%!&amp;: throogh ennfaet; fp sa ?p.#yTe$um W^M'^ ^ WÍHCr' au te aiiovemeot ionod monomers, p the presence of a diáin tr&amp;nater ágens which es dodeeyl mercaptan.

Cnötetefy>;to áí ΐ-lïtr© toáeior, igmms éihlpdíndleű m ater ans! 5,5 grams oî sodtgtp dodeeyl sulphate are weighed, The ssaatesis reactor is then heated tu Ki'(. ί· 2ύ€. Πη η g t in. ι 'κ ^ pie eivAioa is pice, *.v 01 >b e » , > lowing 5 N \ t\y - 116.8 grams of bipermoted waten r, 1 en gjnm\ oívsihum dodeew soiphmc, nggn gî-nm of dodecvl rneveaptam which is 556 ppm of mercaptan reiat-w; to the mass of ah ho engaged mmsaiwcs, - 88.84 grams ofmethaerylk acid. - 13t.; grams of eth> ! acrylate, 30.0 grams of niacromonomer, O.S gram of ammonite persulphate is then weighed, dilated in: d; granm of hipeftetiil wafer for the first catalyst, and 0.08 gram of sodium metabisoiphite diluted ip. 4 grams of bipenmited water tor the second catalyst. When the synthesis reactor is at the required tetitperatPie both dtelysts are added and priymermaiion it ond tetem for 2 If op at 8-i if T i . with MmuUaneous addonm of die pro emols.on, fhc pomp vs tubul si oh 20 grams of hi permuted water, and is cooked for t boor at Kd'C 4.- .230. Finally it is eooledtat rpte temperature and filtered. 18:332.4 lilts test nhssiraws the invention .tod use-;. a HASK-type asset utive thickener according to the awottlmn. which ^ a pohma consisting, tu S by si eight ofesash of u\ oionorners, oft, a) 35.58¾ id: niethacryhc aefiv b) 52.5?« of ethyl acrylate, cl 12 ten. Kq'a nK>qomcf formula (if in 11 inch' m ::: 25, η ::: 0, EO designates ethylene oxide, 11 designates the methaeryiaiegixmp, 1Γ designates the group of formula (If i where p t g m ICL r::: 0.

This monomer was ot.nai.ned hy othoxykthon of the commercial product Liai 123.. end then made pohwrteable hy funcUtfnali'iaitfm using a methacrylate group, hthoayiatioB

Ipowp to the skulled man in the art. The same applies to 11¼ tunetionaliration. ’ h'o P< ν' ct s' as o'oiamui Heoech ,oahk( tu a Kati ό medium whkh is \>atei, ol all the ilivesndhtèhdil monomers, in the presence of 560 ppm of a chain transfer agent o-hi eh is dodecyl mercaptan.

Os asoîhtsi N vas accomplished as indicated m test tr 3 , I.c5i..u::i

Ihn toi ilUrstmun tire Imemn-n and uses a HA5fMype associative thickener according: to the invehiion, which is a polymer consisting, hy % by weight of each of its monomers, Ο li a) 35.5¾ to' methacryiic add.. b) 52,5*··* of ethyl acrylate, ρ| 12,0!h; of a monomer of fbrÄlä'{%lil;ÄlÄ m -· 25, « “ 0, BO designates ethylene oxide, R designates the methacrylate group. R" iVoanaCCN me at ottp > a tonnáin {Ü) n In, ; a p ρ 10, r O.

This monomer teas obtained hy ethoxylation of the commercial product LÄ 123, ghd then made polymers tahié b> úsnetsonahrOion using a methacrylate group- hthoxx façon is undertaken by methods odl las out to the ski Hoi man in the art, rite re ce applies to the Innciksnaiieathm.

This piiymef was obtainedihmttgh coatael in a maetive 05 the abovementiooed monomers, in the pscs„nee *4 "'BO ppm ot a eham nut^to ,g cm ohieh ts dodecU mete iptan

Its ssmd'esïs vs o acv-miphecot a·-, khonted m res' 3

IkiUilâ

Tins test illustrates the invention ;md oses a HASE-î> pe ww.» neuve thîvhooer according to the invention, which is a polymer consisting, by % by weight of each of its monomers, oh a> 34.0 % of methacryik acid, H) 51 0 0§ of etbp t newUte, c) 1 ** 0 % ol a munomu ot fo?mol 1i1). nt winch, m A\ n t\ \ O deaigUi'tCN ithtkme ox nie. R designates She mnhaen Lao gtonp. K' designates the group of formula (It) where p * q ·=· 1 ft, r ::: 0.

This monomer was obtained by e*Ntvd ***ot\ ot the wmm.vma.. p'odoet ltd 'C"« arv then nude polvtaenrahle *>v tuneitonatteanon esnie ..j metkau \ law group. I thox\I,mon is undertaken by methods well known to the skilled mud irr im art. The: sathh aftfhes te the lunofionalpadon.

This polymer was obtained thmt# «putuef ^Inof ail •the sbovementtooed monomers, m the presence of 560 ppm of a chain transfer agent which is dodecyi mercaptan:

Its synthesis was accomplished as indicated tn test tr' 3.

The Brookfield™ viscosities to 10 and f00 revolutions per spin the pf rook 10RFM. Btook uuReM o, mhast, vermetsM (tn ΚΛ 1 md IOÎV, use the mho between the RnvhficUI!S' v.vootv n .t' tvohmoos m.nmc and th* U I,v xwemats, are given m table 1.

Vliese lONUlts demonstráló that ihe H Λ SP pohmos's m S'-·' mmmtioo ». nable a more marked Newtonian pronie to be obtained tbmi with the HASE polymer of the prior ort of referenced RM 5. neb a nm*h prestos thickening offtc.KV -U a limb slieanne. gmbsv'nt ih femte of the Newtonian behaviour, the performance of the product Rheoteeh™ 2100 eeehn img * ks nkm hmieuyo ο» <*id ttswcsotiopi \„d?i oonsoi Ik if elseositf, E sample 2

This lest illustrates the Op aneruamv o* ^evntAi t'uckeueu' yerndung to fU invention, with a view to thicken an aqueous pel. It notably illustrais.·'! the influence of the *4 oo of V an vinivka „v it n .picric" v*. or u> i u. eu * h». x iji i.H «fct

For each of the rests m' κι 12, a fixed mass equal to 10.7 grams of the thickener for testing, together with approximately I gram of a neutralizing solution of ammonium hydroxide at 2Kÿ. H iutmdqeef into 215 gr&amp;» iqyepus .glutton consisting of to mams ofdtaomsed műm amt t ?5 mmoa of an aery ke hűidet N corny! Xk 00 sold In the company DSwFA :touo !h N «cm t.hramm fV prêt ao and uses a lit. R η ν' .uve ame thwkenet n d hs On company CXMTEX:T?* udderthe name Coapur™ 2025,

Ijyf 0.:.1

Him test illustrates the im cohort and uses a IlkSfc-tyin associate.. e ihiekener aceo-almg to the invention, which is a polymer consisting, by % by weight of each of its monomers* of: at 15.57¾ of methacrylic acid. hi 52,5*'·.. of eihxl am mate, el 12,0*0 of a monomer of ibtmuhMlk in winch; m - 25. η « is f.O designates ethylene oxide. R désignant the methacrylate group, fk cesic,κι tes tin snoop ot to'Muhit Hi whose p q n, s <i

This monomer was obtained by tahoxy bison of the commercial product then made nets mctirahie bj. functionalisation using a methacrylate group. Lthoxviation K eadu 1 \ wisv-tl'K on > I '\i h d ma i i« mo «r u re mmroto the funet iouuheatiom

This polymer was obtained through contact in a reactive medium which is water, pt ah the abovementioned monomers, in the presence of IJH2 ppm oi a chain transfer igehl which is dodccyi mercaptan·,.

Ita-lpthdsli seas aceomplwhM» :i:odipa:tedu:ni:teihft:S 3. ITn ;rot >11 usina os the ouenoeo and uses α Π·\\Γ'Ρρ&amp; associative deekener .mcorpmg to the nr< ention, winch w die same peonies ,o the one nnpientented to test « 8 "Dus polymer was obtained through contact in a. reactive medium winch is water, of ail the : ahóvemumioneá monomers, u to*. ρ cv'tcv. ot , 04¾ ppor of a cl«gisnsthr ageot which is dodecyl mercanlan.

Its synthesis was accomplished as indicated in test if' 3. iMûllfi

This test illustrates the rovotrd^iii'is^ a; IdÄiStyp assictative thichesmr aeeordmít ti the invention, which is the same polymer as the one implemented m test 0* 8. 'Uns polymerwas obtained through contactm a reactive medium which is water, of all the almvepiehioned monomert, in the preifnee of 2 J4Ö ppm of w chain trapiilf epet which is dodecyl mercaptan> its ssntinww was lecomplished us nidwated in test rf t

This test íllnsttates the mveiloh aiid uses a HAS E-type associative Ihickenet deeoydm^ to the mu mum, w dich w Hie same polymei as the ore implemented m teat n y 'Uns polymer was obtained through contact in a reactive medium which is water of all the atvw mentioned menmintw m rhe picaenee ot 4,1 on ppm of 0 chain mowtet ^vvst which is dodecyl mercaptan:.

Us synthesis was accomplished as indicated m test if·' 8. IäIJIÄ ms iéfllÂi lifestysiasâ â BliiE4|p àssaciaùvc tldckeoer according # -¾¾¾¾ the same polymer as tlc ooe implemented in test n0 B.

Ih'vpoKrc» w ^ obt mwd dooaah ,o naet n t et ne moh \^l a tht Wi the abovementioncd mcaonters, hi die |feseûee #1'5,600 ppm of à chain transfer igent which is dodecyl mercaptan.

Its synthesis was accomplished as indicated in teat rr" 3.

Thu Brookfield™ viscosities at 10 and s00 revolutions per mmute. Stwmer™ and l'CFM, hU the t.mo between the Brnos odd™ sOs-odt) n Itt H\oU,oeu\ f\.r mmuv and the föl™ eisoosliy^ ire gyen ih.fable 2.

Apart from the lief that f&amp;is: fible eordimiéá to demonstrate the capacity of the polymers according to the invention, to thicken an aqueous gel peer a wide tätige of shearing gradients, is also illustrates the influence pi die rate of cMp transfer agent on the rheology of dus geh

Tito value of the Brookfield viscosity ratio at 10 revolutions per on nmedül viscosity is widely reduced when this rate is increased: one obtains a behaviour winch is very Newtonian, dko optimum cotnprotnise hetweett this ratio and torkeegmg the ICI viscosity at a high level is obtained lor tests 9 and 1Ö. which illuaimti the preferential variant of the invention. According to dns venant, the testdts of the HR’R thickener of the poor art ate improved itt terms of the Newtonian behaviour, but above all of the thickening performeh M § high shearing gradient.

Exa difiid I: lids (esi illustrates the tnventtotk ;dÂ:::;$tÉ 4mpknts:iiil a chain hMÿflr agent, and concern« an aqueous emulsion of a polymer consisting of, in % by weight of each o! it? mounmorst a) 35,5% ntethaeryhe acid, hi 5.15% ethyl acrylate, e) id P% oi *v u\>. w t ' nia (Π nt -wuch t* '*> s 0 Í 1 » d^soumd », iÉbylene oxide. R relates to Ä methacrylate group, R! designate^ri^bup-iférmîila (il) with p * q ~ 9, r ™ 0 (designated by the oxo lenn frOyd.

This polymer obtained by contacting all of the ilq^mentioned monomers tn a reaction medium that is'water. Its svnthC'U.·» corresponds to that described in tests No, 14-. to l d, but withoutimplemenhng the chain transfer agent, T.hsis.No;..j.4toJ9

These tests illustrate (ho ityemiou, and use an increasing dose of a chain transfer agent winch ta dodecyl mercaptan (preferred variant of the method of manofaentre according to the present im emiog| and«Mp^ï· of a polymer consisting oh in % by weight of each of its monomers: a) 35.5% methaeryiic add, b) 32.5% ethyl acrylate, et 121% oi a monome* nah tonmda (I.) tn which tn ht. n - 0, R> designates ethylene oxide, R relates to the methacrylate pbup, E?'-dbàipSÂ;^up'Âan (II) with p r q * % r * 0 (designated by the oxo term €{;d:.OPb hus gohmet w.v> oh tat usd b> eontaotmg tn a tcactmn medium that >s vwdeg nil «η aboemmontldned maite-ffl the presence of ή eertaitt quantity of RPhain if ahntet agent: which is dtxfeeÿl ntereapian.

Concretely» for the synthesis of the pdipier m Ü# ptso» of S) ipptn of »reaptm (test .No. Hi one begins by weighing in a 1 fibre reactor 409 grams of bipexmuîcd water and 5,6 grams ol'dodeeyt sodium sulphate, if is heated iá a aphlteiis mauior nr E2*C *. -5¾ 5 '

Dunug fine now a pro enwHoo -,s own, a cd b> ootghmg m a beaker s 116.8 grains oifepxmmsied water, - 1,96 gram of dodecvl sodium sulphate, ·> CU If gram of dodecy! mercaptan, i.e., 556 ppm of mercaptan with respect to the mass of all the monomers Involved, - 88,14 gthms of meif acrylic add,. ., 13 !. f grams of ethyl acrylate, ., 30,0 grams oimscroruormmer.

Next. 0.8 gram of ammonium persulfate ig weighed ind diluiidin 6 pMidfbipepÄed oxter lor the In st catalyst and OM gram bfmëmmtïMâyimâÊM il dlltilM Μ 4 grima of bipermuted water tor the second catalyst When the: SpShes® tmztm is »Ï temperature, tbi 2 catalysis am added andpolymertsiaPon φearned: oof 1er 2 boors at pFC se "FÇ with the addition In parallel of the pre-emulsion. The pump is rinsed with 20 grastet of hipemmted water and cooking is continued tor ! hour at §4°C * "Γ€. Finally, the product is cooled to room temperature stud filtered,

Fbe syntheses t orrvaponding to teats No. 15 to H are earned ont sn a umuL.tr anmnei by adjusting the dose of mercaptan, ÛkoryMions

If is observed that only the tests involving both the particular oxo akohoHxtsed monomer anti the chain transfer agent lead to low BrookfteklTSS viscosity values, even at > ' tK etv.au ofb'' > «p.dsK 4),

In ,,dd; taon each of "'use , umpleteU pm-ueun mixed enudsiona cftoeln eh thicken·* tbs' acrylic binder solution (table 5). The best results are those obtained according to the emulsions df tests No, 17 and II which, while having § &amp;oe|bddTM viscosity measured m 111 hPM that is leys th&amp;f |0|S# ipPa.s for &amp; solids content that is however equal to 25V rewsmeh'-w Nod to a ,ng?bdentt dncvccmg, turn;dons H the sU.u gradient

Uso ικ η \V * h mo θ' »bi '»Τ' Si^ *l J 1<V 0 '1 tl* 5 solids content with a oanmamfaf döÄ5||,. ipypif phssimls, ^smI 1-1^¾ íjísb edvwtageously thicken

JmM&amp;M

This iÄ iiaslrdlef the irweution, It notably mpißPXß^ ae associative monomer differau from the one used previously (meihacryUtfethane hnk).

It imglœe ItCertain ptmify. which is dodecyl mercaptan. ami

Idncefel id rapes Oältdsioo df d polymer consisting oh m ''>· by wet gin ot each el its monomersc a) 35,5% methaerylle acid, b) 52.5% ethyl acrylate. c) ! :2.0¾¾ of a monomer with, fennel a (1) in which1 m - 30.; η ·:: 0, B3 designates ethylene oxide, R relates: to the methaend-urethane group, S3 designates group formula (0) with p * g -5-:¾. r lois pohmet ne° obtained U oootactatg ali U the above-mentioned monomers in at V action modi on dsn h v, m 1 at con. Hop s \ tin wax' pox os> dtsoohed ..·<$ >». r. <;'.·%

Tests No. 2 Uo:d23

This test diud rates hue invention ft notably implements a different associative, monomer írom the one used in the previous testa t similar to that used In tests No 14 to Hb hot o\> ethylated do times. the % of fer associatee tncmomei isme being 10 <}.ud feU)

It Implements a emtain gaaruitv oi av^^i^gg^r aient which is dodecyl tnercapiatv, : and : ipotmems an npeous ; emulsion of a polymer consisting oh in % by weight of each of Its monomers: at 23.2 and V5 s \s no lixxuylx .xfe (tests ό .md loi b) 52,5% ethyl acrylate. e) 10.0% and 15% of afepnomcf No. 21 and 22) m - 25. « O. KO designate ethylene ovale, R relates u> the methacrylate gionp. R* designates group formula sift wfc|: 11 I î sfe ο» :|g

CuFOis).

This polymerwas-obtained V\ uuHaetmg all d th* unos *-Mentionul monomers m .1 „*u, ,vn !\ùrsr mas \'<uuei uummme, fo :}vp s o·» *v , V* pn‘"S' s s &amp;££QÍÉÍMv I he resold uecordinp to tests 2d to 22 ^onohotud those obumed uiootvtmg to icmn No ; o so Id Loss Hrísoktkidm visoosvües aie observed. ftÄ'ÄÄÄ premeuhalMed Âôkèeii'^IMé HASfe typo. sÄk áj# Larfliälil© tor a ••söMtáS'.. .hößtfßf '«Ä? s- .iprtmgrdaT interest, devoid ot nonil phenoK and that can advantageously thicken a latex in aqueous solution. lMlNp.Jl.to.27

These teats dlusimfo i« outside Of she invention, They notably implement an associative monomer that is different from the one used in the previous tests, and: h'e© of oomlphenoK Thes nnplemem (u-ds 25 to 2Ί or do not naplement (tests 2? ansi 24i 2.1 tO ppm of a chain transfer agent which is dodecyi mercaptan.

They concern an aqueous emulsion of a polymer constating of, in % h> weight of each of its monomers. at 35.5% methaerslic add. b) 52.5% ethyl acrylate-» c) 12.S % of a monomer which is; a monomer with ,fcmu!u,.{i) in vs lech m ~~ 3ft, n 0, FO designates ethylene oxide, R relates tv the moth -> -me group» R' ίο%,> to ""hoed ' dootxumd tbi test No 23 Ideslinated by the term iso t %£0>), a monomer with ionod.! <T- ο, wb,,o m %, a U t O 'dales to condone ovié» R relates to the methacrylate group, R' designates a linear alkyl group with 12 carbon atoms for test No. 24 (designated hs the term 12 diOs 0- the same monomer as that according to test No. 23 for lest No. 25;

i with nmmtla il't m wtuch m 25. « - if ko designate^ othfoerse o.vJe. R to te met! <u.m ,,e gump R klito-V unep o * .nb m ato? tor test No. 26; the same monomer as that according to tes! No 26 for tost No. 2"; *!«s particular tost implements 5.6b0 ppm of ittereapkm:.

Tins pcA “no! w.h ubfmvd h\ evmwUn;.; ,il oi the ahm c mentioned mmiomem m a ffàeiton medium lkat is svalor according to

OhlMVMM h is ebsem eo c. eoidu''' to ks»u V> 25 to 2". that the dwu' m > mmtonvr no* melodcd in the un notion, or foe choice to not use a chain transfer egem. leads to BrookfieldiM vtsefoify itkeMiibki at 10 RPM that nsevery quickly in accordance forth the solids conteni: liklte of these esuolsio:os is tltcrctbre suitable tor pp-neoiralmation due to the consequence ni. being me \ t&amp;cous.

By comparsnii between tests No. and 27 ihat implement the largest quantity of chain tranisflr pgeni i 5,660 ppmt, die very hostmmlis ap touuiiwtfo the entulsiort aeçonltng to the invention ut tenus of rheology at is, \t h tests \i ^ 7" "<iu untomé vat diced no" vie foe emeB ow-aws m , solids content of 20%, they emdd not. he tested on foe acrylic binder.

IkfoHu.......21

This teat ||lpstrate|: ag: :iat;oa optsidd of the ;inyin|pn. andiintplcmihls an emulsion of a HANF polvmer marketed h> the CO AIF.VjM cmnpum undet die um« RheoUvh! M ? ! t which contains nonylphentds,

CäMlÄlÄI

Very lose Brookfield™ viscosity values measured at 10 RPM are observed, even at 25% Sidtits eoment, -,-, we'd a'. < evrkec thtekovmg power en the hues binder, regardless of the shear gradient,

Nevertheless, this es-nulsion contains nnnyiphenols. lS:Siv.N;i..2y.as)d..;íO.

These tests illustrât© ait &amp;rm oshMe of the ioventioo api implement au eotutsios of a E4BII pdemef marketed seder tip namos AorpoP'^ TT $|!> and AerpoPAi TT 935 Iw th© EOI-IM û BAAST© oumpaoy #M do hot contain Iho particular mottosior pf the present imenüon. ,,Ûkgà»

None of thés© eotulsíoas are aahsíaeforv in terms of The viscosny as ts: the l3mokÍÍeltPM viscosity tneasured át 1:0 ilFAf delag extsonsety Mfh* even In &amp; -solids content of iW»< They were out tested on the sorylic hinder.

In light os mm last uHe, st is noted that the emulsions according to she invention .dfov· the tonnulator to obtain a tango of highly varied ideological hehav tounx

Example 4

This test Illustrates the implementation of sasod ah^e thickeners aççdM&amp;iÉ? ' tlLNSEu and according to the invention for the purpose of thickening an aqueous gel Ihat each of tests No. 3! to 33, into 215 äquiSM-Mltlth« ii parhs of deionixed Äteftahd lît grauN of u Neoetv! AlS. iCf aerglli hinief marketed hy ite;13iM:?:S!S company is introdpegd a fixed mass equal to !0p gramt of Éi lfdekeoef to he tested as well as about t gram of a of 285¾ ammonium hydroxide neutralizing1 ^oluuor Has ριοΐοαΊ ts nlentieat tu that dosen bed for es ample No I. iMililJiisJI,

These tests illustrate the invention, and implement an increasing dose of a chain transfer agent wntoh o if ι ο,. > nebcin ! m atom vanett ot *K a m w ot mannt ^tut according to the present invention), ami concern aqueous emulsions of a polymer consisting of. in % by n eight of each of its monomers; a> 35.5% methaotyhc add* hi Ά ν' i ethyl acrylate, c) ! 2.0% of a monomer with iormula (I) in which 10 relates to ethylene oxuic arid PO relates to propylene ox Ide. R relates to the methacrylate group» P' relates to group; formula 111 s u sth p q =· *1 r it {designated h\ the >. < <.o let a» 1' ' EtK 1. "Λ nh m ::: 50, n : I* tor test No. 31 m " ΊΟ. η :;· 10 üu test No. 32 m IS. a 0lortpf No. 33

Those poh noon ««« nhubtred by contacting m a teadem romina a that Is water all of above-mentioned monomers m the presence of Sod pom of dodaeU mercaptan. In comparison with tost No i-1 dv number of units of ethylene and ptopyiene oxide are varied here. I he Brook HeldiX' et lu .ad lut* ROM < Brook HtRPM. Brook jtMUPM in mPa A Stornier^ (.a Kl 1 and h Hy down s es a.s well ,o the relationship between the lhookíte'díM --. oco-oü ,>t |o K PM .eut do ddl wete seperted os t die o

These results demonstrate trust the BASE polymers of the invention protide a more ntarxed Newtonian pm!*}? than that with the HASE polymer of the prior an referenced R M X wuh a much greater thickening elYseieney at high rheas' gradient. ot me lesei -d me Newtotmni nature, the porlormanee of the Rlte>eedriy' .toit product 'stunning amyl phem.sis is est lean equalled. and it is greatly intpror ed in terms of the ICI r iSvOsity. liapl

This lest illustrates the implementation of associative thickeners eecmrdipg to the prior $$ i RASR nnd aeootdmg to the invention for the purpose of m m§#mïm pl> ;fiaÄ of tests lib, 14 to 36, into 215 grams of an a|ieons oolöinn, ôéi|ïiih^;vë:C· of dekmkæci wideband ]?$ grams of a Neocry! XK. *>0 acrylic binder marketed to the PSiM*** eompaov is onuxlmed a tked mu*.\ equal to 10 grams ot the ihtekenei to bo tested 8.¾ well, m about t gram of a of Z8% ammonium hydroxide neutralizing, so kit ton. This protocol is identical to that described for example No. I.

Tests No 34 to 36

These tests illustrate the invention, and use an increasing dose ol a chain transfer agent which is dodeey! mercaptan (preferred variant of the method of tmmtdacture according to the present invention}» and concern aqueous emulsions of a polymer consisting ok in % by weight of each of its dibnomers: la) 38%. 36°« and 33"<, m'roethaerylic acid for tests No. 34, 35 and 36 respectively,; bj 57¾. 56%, 54%, of ethyl acrylate tor tests No. 34, 35 and 36 respectively e> N\->. H% and 15% for tests No. 34, 35 and 30 respectively of a mm tonte? with formula (!) in whseh TO desifmates ethylene oxide, m Ä 30, u 0,M designates the methacrylate group, If' designates group iamnda flit with p t q - 0; r ~ 0 nlesymated be the o\<^ term 1' 4 O j

IboNc potomét', ouc obnmxxi b> cent amg m a u acton. medium the. ts a a ter all of above-mentioned monomers in the presence of 560 ppm of dodeey! mereaptam In comparison with test No. 14, the monomeric ratios are thus varied here.

Mu. IbookftekPss ομ.όνόο'' ,t "0 and N'0 TPM trimoi Hit PM. ibook UXkPM m mPa.sl, Mormuri^ tin K.U3 and K1iSi viscosities, as well as the relationship between the Brookkeft™ viseosuy at in RPM and the ICfT&amp;s were reported nt table 7.

This# .àsgââ&amp; 'thai the Η Λ S fr. polders ui the invention provide a more marked Newtcmitm proite États -État vviih the HASI:, polymer of J he poor art referenced RM 5. with a much greater thickening efficiency at high shear gradient.

At the level of the Newtonian nature, the performance of the R.heoteeh'm 2100 product containing alkyl phenols' is as least equalled, and it is greatly improved isi ternis of the fO viscosity.

Claims (3)

1. (!) képktü mommsen R-iAOk-<BOyRf öl: ^ es ή egész szám és értékük ki&amp;efcfeipipi Í 5Ö^fegüláBb égyiÍük értéke nePiouflá, < és B jelentése 2~4 ögpÉSlii különböző alkilnaoport, ΛΟ esqpgrt tetemeseele-riVose« etslén-oxid, és BO csoport jeUmtéae előnyösen propüén-oxtd, t jelentése tblűetlen ptdimeá^áÍMté^^pf^tfönpse, metakitiár, :;' jelentése aE*tl ¥«iÄme«v% l»gy legalább ogy (I!) képien! csoportból áll: Cl !?"(€!' \> y€ 1 IKlíásCHyCíby al p egyikak értéke nem nulla, és 5 < p * q < 13, r egész szám co rn 0.

2. Az 1. igénypont szerinti monomer, * hagy n - % AP plentése letuoxid, és m értéke 20 és 40 kűzött található, :3i Egy f-f ASE-típusú polimer, amely az alábbiakból áll: li^akriisav, a (met)akrtlsav legalább égy észtem igga!Ésb «gy (1) képlet« monomer, E-(AOp5r(BO)s-ir ok « és n egész szám és értékük kisebb, mint 150. legalább egyikük értéke neat nulla \ es B : ok ütése 2-4 szénatom* >s eg> maste* különben, ulkslcsenm, Ai5 esop-u* a* ornese Co-nyosen eidéteoxkl, és BO csoport, jelentése előmösen propi íén-oxid, < jelentése telítetlen polimerizálható csoport, előnyösen metakriiát, C jelentése el»» jellemezve, hogy legalább egy (II) kópletü csoportból áll: CHriCHjVCiïtCll'JïCHi-tCI-li^- io! p és q egész szénás legalább egyikük értéke nem nulla, és 5 < p q < 13, ? egész szám érke 0. 4< A '3. igénypont szerinti polimer, aztsii|illiÄM^.Äopr mindegyik a saját monomer âlk i|' 2Û% - 305% étöpybáép 35% «· 453·% CmeBgkril %$\% h)'4®%.* ?(Bé$ ûmÿQàm 45% -5353% (s%%4kn|sà;v %|a!éob g|y%|%oros o) 2% * 2.0%,. elipy&amp;en. 334 * :!!%% kptâhh egy (I) KopIdtümtonöSier, 5. Λ 3 s agy 4, igénypont szerinti polimer, azzal J«li*í»e«ve, hogy a/, ti) képiem monomerben n - Ο, Λ.Ο jelentése eülén-oxld, és m éneke 20 és 40 közötti. 6, kijárás %A5i.:-í;pu«o polimer előállítására, egy reakció etegybeo az alábbiak érintkezésbe hozásával : a) (meOekrilsav, b) à {metjákíílsf¥ legalább égy észtem, c) legalább egy (1) képiéül monomer, íUAQWrBOVR' abob - rn és n égésé szám és értékük kisebb, mini 150, legalább egyikük értéké nom nulla, ' A és B jelentése 2-4 szénatomos egymástól különböző alkilesöpört, ΛΟ csoport jelentető· #j§* nyesett etllén-ozid. és BO csoport jelentőse előnyösön props ién-mrid. - R jelentése telítetlen poli me tárái ható csoport, előnyösen metakrilát - R'jelentése azzal v&amp;n jeliemezve, hogy legalább eg}' (ΙΠ képlete csoportból 111: Ok · (C I b)?-CH(CH%re% r(CH?):r ahol p és q égésé szánt és legalább egyikük értéke nem milia, 5 < p q 13., r egész szám értéke 0, adott esetben az ab hj és ej összetevők érintkezésbe hozása előtt és-vagy alatt és/v&amp;gy után legalább eg}' lármámon szer hozzáadásával, ?. A % igénypont szerinti eljárás, stzzal jellemezve, hogy az átadó szert alkalmazzuk és amaU hogy a reakció eíegyhe/ hozzáadott tömege 1 500 ppm és 4 000 ppm közötti az. a), b) és ej összetevők teljes tömegére vonatkoztatva. 8. Λ 6. vagy ?. igénypont szerinti eljárás, azzal jellemezve, hagy az (!) képiem monomerben η ~ 0, ΛΟ jelentése etilén-oxid, és rn értéke 20 és 40 közötti. V. Λ 6%. igénypontok bármelyike érinti eljárás, azz^l jdle&amp;tsátve, hogy a reakció elegy egy másik oldószert kmalrmtzö vízből, előnyösen csak vízből áll.

10, .A ő'V. igénypontok bármelyike szerinti eljárás, azzal jellemezve, hogy' a lánc aíadó szett az N-dodoeil-rrmrksptán. N-decil-merkaptán, oktibmerkaptzn. I J-rlir.tmrkapto-aA--dioxaokíün (DMOO, n° CA% 14470-87-?), thnvjsas közű) választjuk. ï A 3'5. igcaypoïUok bármelyike szerinti IIASIMipusû polimer alkalmazása süi i-tÔSÂrként viz.es kèsziiméoyben, 12. A. S"È Igénypóotök MMtéiy íke sztóttl HASIMlpissu pôilMért VäIhmzo vizes. készítmény, aææal jellemezve, hegy az vizei lesték.