CZ334598A3 - Výroba rozvětvených povrchově aktivních látek - Google Patents
Výroba rozvětvených povrchově aktivních látek Download PDFInfo
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- CZ334598A3 CZ334598A3 CZ983345A CZ334598A CZ334598A3 CZ 334598 A3 CZ334598 A3 CZ 334598A3 CZ 983345 A CZ983345 A CZ 983345A CZ 334598 A CZ334598 A CZ 334598A CZ 334598 A3 CZ334598 A3 CZ 334598A3
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Description
Oblast techniky
Předložený vynález se tyká způsobů výroby čistících povrchově aktivních látek, zvláště těch, které obsahují hydro fo bní stavební j ednotky s rozvětvených řetězcem.
I
Dosavadní stav techniky
Běžné čistící povrchově aktivní látky obsahují molekuly, které mají vodné' solubilizační substituční (hydrofilní skupinu) a oleofilní substituční (hydrofobní skupinu). Takové povrchově aktivní látky typicky obsahují hydrofilní skupiny jako kařboxylat, sulfát, sulfonat, aminoxid, polyoxyethylen a podobně, které jsou připojené na alkylovou, alkenylovou nébo alifaticky substituovanou arylovou hydrofobní skupinu, která obvykle obsahuje 1Ό až 20 uhlíkových atomů. Proto výrobce takových povrchově aktivních látek musí mít přístup ke zdroji hydrofobních skúpin, k nimž může být žádaná hydrofilní skupina připojena chemickými prostředky. Nejranějším zdrojem hydrofobních skupin byly přírodní tuky a oleje, které se převáděly na mýdla (tj. s hydrofilní. skupinou karboxylatem) zmýdělněiiím se zásadou.
Kokosový olej a palmový olej se ještě užívají k výrobě mýdla, stejně jako k výrobě alkylsulfatové (AS) skupiny povrchově aktivních látek. Jiné hydrofobní skupiny jsou k dispozici z petrochemikálií, které obsahují alkylsubstituovaný benzen, který se užívá k výrobě álkylbenzensulfoňatových povrchově aktivních látek (LAS).
V literatuře se prohlašuje, že určité rozvětvené hydrofobní skupiny lže s výhodou použít k výrobě alkylsulfatových čistících povrchově aktivních látek; viz například U.S. 3,480,556 de Witt et al., z 25.1istopadu 1969. Avšak.je zjištěno, že v beta poloze rozvětvené povrchově * aktivní látky, popsané v tomto patentu, jsou horší kvality .ve vztahu k určitým parametrům rozpustnosti, jak je dokumentováno jejich Krafftovými teplotami. Dále bylo zjištěno, že povrchově aktivní látky, s rozvětvením blízko středu uhlíkového řetězce hydrofobní skupiny mají mnohem nižší. Kraffiovy teploty. Viz: The Aqueous Phase Behavior of Surfactants, R.G.
Laughl i n,. Academie Press, N.Y. (1994), str. 347. Podle toho bylo nyní stanoveno, žě tyto povrchově aktivní látky mají přednostní použití zvláště za podmínek praní za studená či v chladné vodě (např. 20 °C až 5°C).
• · ·· * « · • · ♦ ♦ • ······» • φ φ · φφ φ ·· * φ • φ
Jedním problémem spojeným s výPobou čistících povrchově aktivních látek s hydrofobními skupinami s rozvětvením ve středu či blízko středu řetězce je nedostatek pohotového zdroje těchto hydrofobních skupin. V předloženém vynálezu je popsán způsob výroby takových rozvětvených hydrofobních skupin a jejich převedení na ve středu řetězce nebo blízko středu řetězce rozvětvených povrchově.áktivních látek.
Podstata vynálezu
Předložený vynález zahrnuje způsob přípravy alkenů, které jsou rozvětvené ve středu nebo blízko středu řetězce (zejména rozvětvené methylem vé středu nebo blízko středu řetězce). Tyto látky jsou pak použity jako základní zdrojový materiál, který poskytuje hydrofobní část rozvětveného řetězce čistících povrchově aktivních látek.
Tento způsob je popsaný následujícím siedem reakce. l)Dimerizace 1-alkeriů gh2
RCH=CH2 + R'CH=CH2 -► R—CH2CH2—R· (|) a
R’CH2CH2-G-R kde.R a R' jsou stejné nebo různé něrůzvětvené alkyly a kde R je Cj ažC7, s výhodou C5 ážČ7 nerozvětvený alkyl a R' je €3 až C7, s výhodou C.5 až C7 nerozvětvený alkyl. Pro použití v přípravě povrchově aktivních látek v čistících výrobcích jako jsou prací prášky, kapaliny do myček nádobí .a podobně jsou· R a R' s výhodou stejné nebo se jeden od druhého liší jedním nebo dvěiha uhlíkovými atomy délky řetězce. Některé přímé álkeny také vznikají dimerizací a tyto.se případně oddělují za použití molekulových sít. Krok 1 tohoto způsobu je uzpůsoben pro zisk rozvětvených alkeňů, které s výhodou obsahují celkově od 12 do 18 (vprůměru) uhlíkových atomů.
.2)Výroba alkoholu
V kroku 2 (Postup A) še směs alkenů pro krok 1 znáhodrií pro zvýšení konečné tvorby alkoholů (i) a (ii) v následujícím kroku 3. Nebo (Krok 2, Postup B) tento znáhodňovací krok lže vypustit a Oxo katalyzátor sám znáhodrií konečný produkt mezi třemi možnými konečnými stavy.
lífl ři>
Postup A (i) (1)/(11) > Náhodná vnitřní směs alkenů (RIOM) (ii) RIOM co/H2:OÍto kalal^ Směs rozvětvených alkoholů nebo
Postup B (1)/(11) co/H2,oxoka[airzat<„ Smésrožvětvenýchalkoholů
Oxo proces pro výrobu alkoholů je detailně popsán v Kirk-Othmerově Ericyclopedia of Chemical Technology, 4. vydání, svazek 1, str. 903 až 908 (1991), Jacquěline I, Kroschwitz, úřadující editor, Wiley-lntěrscienee, N.Y. Katalyzátorem pro tento krok je například kobalt-oxid uhelnatý-organofosfín.
Směs alkoholů z kroku- 2 předkládaného postupu zahrnuje sloučeniny rozvětvených primárních alkoholů následujících vzorců pro použití v kroku 3, uvedeném níže.
CH3
I
i.) R- CH2CH2CH-R -CH2OH a (fH3 ií.) HOCH2-R-CH2CH2-CH-R' a menší množství (jlhClkOH lil) R-CH2CH2-CH-R'
Rozumí se, že když je na R nebo R' substituována skupina C11?OH, jé tato primárně na jejich v pořadí koncových atomech nebo v menším rozsahu ria jejich předposledních uhlících. Je žádoucí, aby v kroku.3 byla přítomna minimální množství.sloučenin.vzorce (iii).
- 3) Výroba povrchově aktivnblátky SO3
Směs rozvětvených alkoholů * Rozvětvený alkylsulfát
Uvedený způsob s výhodou nemá za následek gemínální rozvětvení, to. je vznik kvartérní uhlíkové substituce. Sterická překážka blokuje inverzní adici na vinylidenový uhlík účinkem kobállu-oxidu uhelnatého-organofosfinu, která by jinak dala vznik nebiodegradabilnímu kvarternímu uhlíku. Navíc še málo objevuje i vicinální rozvětvení (méně než 3 %). Samozřejmě část z celkového zdrojového materiálu zůstane nerožvětvena. Uvedený způsob poskytuje z • * « « · « * • ···· · · • *♦ hlediska čistící účinnosti a biodegradabilily typicky a s výhodou v případě isomerů i) a ii) hydrofobní látky s jedním methylem blízko Středu řetězce. Všechna zde uvedená procenta, poměry a rozsahy jsou hmotnostní, není-li jinak specifikováno. Všechny zde citované relevantní dokumenty jsou obsaženy v odkazech.
Podrobný popis vynálezu
1) Dimerizace alkenu:
Před ložený vynález zahrnuje způsob přípravy: prekursorů; povrchově aktivních hydrofobních látek dimerizací dvou 1 -alkenůse stejně dlouhým nebo téměř stejně dlouhým řetězcem za vzniku vinýlidenového alkenu s délkou řetězce vhodnou pro mycí prostředky. Tyto C5 až C10 1 alkeny, s výhodou C7 až Cg, se dimerizují.ža vzniku C10 až C20, s výhodou C14 až Cis vinyl idenovýeh álkěriů, které při Oxo reakci dají vznik Cj 1 až C2| , s výhodou G15 až Cfg alkoholů. Existuje mnoho způsobů provedení uvedené dimerizace; viz US Application 9,200,398, US 4,658,078, US 4,973,788; O. S. Vostrikova, A, G. Ibragimov, G. A. Tolstikov, L. M. Zelenova a U.M. Dzhemilev, Izv. Akad. NaukTokkyo Koho, 06228016 A2 [Chem. Abstr. 122:186930].
2) Výroba alkoholu
Postup A část a) Dvojná vazba mezi uhlíky vinýlidenového alkenu se předizomerizuje užitím inetodz, kterou používá Shell k izomerizaci 1-aíkenů ve svém způsobu SHOP; viz Kirk-Othiner Encyclopediaof Chemical Technology, 4. vydání, svazek 17, str. 848-850 (1996),), Jacqueline I. Kro schwitz, úřadující editor, Wiley-Interscience, N.Y- a Chemical Economics Handbook, str. 681. 5 03 0K-L, Stanford Research Institute, Menlo Park, CA 94025, říjen 1993. část b) Oxo.chemie se používá k převedení předizomerizovanéhovinýlidenového alkenu (nyní převážně vnitřního alkenu) na směs primárních alkoholů, Pro toto je třeba oxo katalyzátoru, který izomerizuje dvojnou vazbu před karbonylací na 1-polohy, jako je případ použití katalyzátorů kobalukařbonylfosfin v jednokrokovém způsobu, viz Kiřk-Othmer Encyclopedia of Chemical Technology, 4. vydání, svazek 1, str. 903-908 (1991). Postup A (v to zahrnujíc předizomerizaci) Se vykonává pro zajištění relativně vysokých výtěžků alkoholů i a ii versus alkohol iii. Alkoholsulfaty i a ii jsou žádoucí povrchově aktivní látky, zatímco alkoholsulfaty iii lze postrádat.
* » • · • 00 * ··· • · 00 • 00 • * · 0 ·
0 0 · • 00 ··· • · · * • •0 0 0 * ·
0· ·♦
Postup Β
Tento krok využívá stejný oxo katalyzátor na vinylidenový alken, přímo bez jeho přédizomerizace. Zde se spoléhá na katalyzátor, aby zcela zizomerízůval dvojnou vazbu mezi uhlíky vinylidenového alkenu před karbonylací. Záměrem je získat relativně stejně i a ii ku iii jako se získá postupem A.
Lze také udělat jiné povrchově aktivní látky odvozené ód mastných alkoholů, jako například alkylethoxylsuifaty (AESj, alkylpolyglukosidy (APG) atd. Je.registrováno, že povrchově akticní látky jiné než álkohols.ulfaty nebo AES se vyrobí oxidací .uvedeného, alkoholu nebo jeho aldehydického meziproduktu na karboxylat (to jest mýdlo s rozvětveným řetězcem). Toto mýdlo může být jako samotné vynikající povrchově aktivní látkou a/nebo složkou mycího prostředku. Tento karboxylat může také být použit jako zdrojový materiál a být převeden na rozvětvené acyltauřaty, ačylisethi.ohaty, acylsarkpsinaty, acyl-N-methylglukamid nebo jiné acylodvozené povrchově aktivní látky použitím v oboru popsaných technik.
Průmyslová použitelnost
Povrchově aktivní látky s rozvětvenými řetězci typu vznikajícího tímto procesem mohou být použity ve všech druzích čistících prostředků. Tyto prostředky zahrnují, ale nejsou omezeny na: granulové, kostkové a kapalné prací čistící prostředky; kapalné prostředky pro ruční mytí nádobí; kapalné, gelové a kostkové osobní Čistící výrobky; šampony; prostředky na čištění zubů; čističe tvrdých povrchů a podobné. Tyto prostředky mohou obsahovat nejrůznější škálu běžných čističích složek. Následující seznam těchto složek j,e uveden pro. pohodlí sestavovatele a není omezením typů složek, které mohou být použity se zde uvedenými povrchově aktivními látkami s rozvětveným· řetězcem.
Zde uvedené povrchově aktivní látky s rozvětveným řetězcem mohou být použity v kombinaci s jinými složkami majícími prací schopnost. Takové složky například zahrnují 1 až 10 pm zeolit A, poiykarboxylatové složky jako je citrát, vrstevnaté silikátové složky jako je SKS-ó (Ilocchst) a fosfátové materiály·, zvláště tripolyfošfat sodný (STPP). Vetšina pracích čistících prostředků typicky obsahuje alespoň 1 % složky, typičtěji 5 až 80 % složky nebo směsi složek.
Jf • φ · • · · · • φ · · · • φ • Φ φ • φ φφ • · · φ φ φ · φ φ · «« · φφ φ » φ · • * * · • ··« φφφ • · φ φ * ·
Enzymy jako j sou proteasy, amylašy, lipasy, celulasy, peroxidasy a jejich směsi se mohou využít v čistících prostředcích obsahujících povrchově aktivní látky s rozvětvenými řetězci. Typické čistící prostředky obsahují 0,001 až 5 % komerčních enzymů. Čistící prostředky mohou také obsahovat polymemí činidla uvolněná z půdy (SRA). Tyto materiály zahrnují například aniontové, kationtové a nenabité,monomerní jednotky, zvláště polyesterové materiály. Zvýhodněné materiály tohoto typu zahrnují oligomerní tereftalátové·estery, sulfonované, převážně přímé esterické oligomery, které obsahují kostru opakujících se tereftaloyl- a óxyalkylenoxy- jednotek a ftaloyl-odvozených sulfonovaných koncových skupin, Z SRA jsou mnohé popsány, například' v U.S: 4,968;451; 4,711,730; 4,721,580; 4,702,857; 4,877,896;
5,415,807 a v jiných literárních odkazech. Tyto materiály uvolněné z půdy typicky tvoří 0,01 až 10 % z konečného složení detergentů.
Čistící prostředky mohou také s výhodou obsahovat bělící prostředky, které zahrnují bělící činidlo a jeden nebo více bělících aktivátorů. Jsou-li přítomny, pak bělící činidla jako. je pérkarbonat nebo perborát (zvláště monohydrát perboratu ΡΒΪ) se typicky používají na hladinách 1 až 30 % z konečného složení detergentů. Bělící aktivátory jako je nónanoyloxybénžensúlfonat (NOBS) a tetraacetylethylendiarnin (TAED) a jejich směsi mohou být použity pro zvýšení bělícího působení látek, jako je perborát a pérkarbonat. Je-li přítomen, pak množství bělícího aktivátoru je typicky 0yl až 60 % z bělícího složení, které zahrnuje bělící .činidlo plus bělícíaktivátor. Jiná bělící činidla jako takzvaná fotoaktívovaná bělidla-.(viz U.S. 4,033,718) mohou být také použita. Sulfonovaný ftalocyanin zinku je zvláště zvýhodněné fotoaktivační bělící-činidlo.
Čistící prostředky mohou také obsahovat odstraňovaeí/protiusazovací činidla jílovité půdy jako je ethoxysubstituovaný tétraéthylenpentamiii; viz U.S. 4,597,898. Tyto materiály typicky obsahují 0,01 až 10 % z celkového složení prácích čistících prostředků.
Čistící prostředky mohou také obsahovat 6,1. až 7 % polyniérních dispergačních činidel, které jsou zvláště výhodné v přítomnosti zeolitu a/nebo vrstevnatých silikátových složek. Tyto materiály jsou v oboru známé (viz U.S. 3,308,067). Tyto materiály zahrnují kopolymery na bázi akrylatu/kyseliny jablečné tak, jak jsou popsány vEP 193,360, stejně jako polyethylenglykol (PEG).
Čistící prostředky zde. popsané mohou také obsahovat různé zjasňovací prostředky, inhibitory přenosu barvy (zvláště polymery N-vinylpyrrolidonu a N-vinylimidažolu), potlačovače pěnění (zvláště silikony), chelatační činidla jako .jé nitrilotrioctan,
999 • ♦ · · · • · « · · · • ···»··· · » « * · · «« « ·· » · V « · 9 9
999 999 ethylendiamíndijantáran a podobně. Tyto iňateriáfy typicky tvoří 0,5 až 10 hmotn. % z celkového složení pracích čistících prostředků.
Navíc se rozumí, že povrchově aktivní látky s rozvětveným řetězcem, připravené způsobem, podle předloženého vynálezu, lze užít samostatně v čistících prostředcích nebo v kombinaci s jinými Čisticími povrchově aktivními látkami. Úplně složené čistící prostředky budou typicky obsahovat směs typů povrchově aktivních látek, aby se získala široká čističi účinnost pró různé druhy půd.a skvrn a při různých podmínkách použití, jednou z výhod zde popsaných povrchové aktivních látek s rozvětveným řetězcem je jejich schopnost snadného složkování v kombinaci s jinými známými typy povrchově aktivních látek. Příklady, které nejsou vyčerpávající, přídavných povrchově aktivních' látek, které lze žde použít typicky na hladinách 1 až 55 hmotn %, zahrnuji nenasycené· sulfáty jako je oleoylsúífat, CioažC.ig alkylalkoxysulfaty (ÁEXS; zvláště EO 1 až 7 ethoxysuífaty), G|O až C|g alkylalkoxykařboxylaty (zvláště EO 1 až 5 ethoxykarboxylaty), Cjoaž Cjg glycerolethéry, C|0až C|g alkylpolygjykosidy a jejich odpovídající sulfátOvarié po.lygtykosidy-a C^až Cig aífa-sulfonované estery mastných kyselin. Také mohou být použity neionógenní povrchově-aktivní látky jako jsou ethoxylované C|Oaž Cig alkoholy a alkylfenoly (např. Cioaž Cig EO' 1 až 10). Je-li to žádoucí, pak se do celkového složení prostředků mohou také zahrnout tradiční povrchově aktivní látky jako betainy a sulfobetainy.(sultainy) Cj2 až G|g, Gioaž C|S aminoxidy a podobně. Cioaž Cjg Nalkylamidy mastných polyhydroxykýselin lze použít také. Typické příklady, zahrnují C|2až Gig Ν-methylglukamidy..Viz WO 9,206,154. Ostatní ód cukrů odvozené, povrchově aktivnílátky zahrnují N-alkoxýamidy mastných.polyhydroxykyselin jako je Cióaž Gig N-(3methoxypropyljglukamid. Pro nízké pěnění mohou být užity N-propyl- až N-hexylglukamidy Ci2 až C|g. Tradiční mýdla Cjo až C2o lze také.použít. Je-li žádoucí vysoká pěnivost, lze použít Gio až C16 mýdla s rozvětveným řetězcem. Alkylbenzensulfonany C i o až Cm (LAS), které se často používají v prácích prostředcích, lze také užít se zde popsanými rozvětvenými povrchově · aktivními látkami.
Následující příklady popisují použití povrchově aktivních látek s rózvětveným řetězcem podle předloženého vynálezu v různých čistících prostředcích, ale nejsou zamýšleny jako vyčerpávající.
| » · » ♦ · · • · ···· • · · 8 · | « ··· * · · · • · * · · ♦ .· • » « · · ··· ··· ·»·* ··· ·· ·· | ||
| Příklady provedení vynálezu | |||
| Příklad 1 | |||
| Granulované prací prostředky se připraví | následujícím způsobem | ||
| A | B | C | |
| Drolivý prášek | |||
| ZeolitA | 30,0 | 22,0 | 6,0 |
| Síran sodný | 19,0 | 5,0 | 7,0 |
| Polyakrylat LAS | 13,0 | 11,0 | 21,0 |
| Rozvětvený AS* | 9,0 | 8,0 | 8,0 |
| Sodný silikát | - | 1,0 | 5,0 |
| Mýdlo | - | - | 2,0 |
| Uhličitan sodný | 8,0 | 16,0 | 20,0 |
| Postřik | |||
| G14-15EO7 | 1,0 | 1,0 | 1,0 |
| Sucháaditiya | |||
| Protcasa | 1,0 | 1,0 | 1,0 |
| Lipasa | 0,4 | 0,4 | 0,4 |
| Amylasa | 0,1 | 0,1 | 0,1 |
| Celulasa | 0,1 | 0,1 | 0,1 |
| ŇOBS | - | 6,1 | 4,5 |
| PB1 | 1,0 | 5,0 | 6,0 |
| Síran sodný | - | 6,0 | - |
| Vlhkost & Různé | Do celkového vyčíslení |
C|2 až C]4 methylem rozvětvený alkylsulfat připravený podle výše uvedeného popisu ♦ A
AAA
AAAA»
A • A
AAA » » »
A · · * AAA
A A
AAA
Příklad 2
Nevodný kapalný prací prostředek obsahující bělidlo se připraví následujícím způsobem.
| Složka Kapalná fáze | Hmotn. % | Rozsah (hmotn. %) |
| Rozvětvený AS* | 25,3 | 18 až 35 |
| C^až C,4, EO5 ethoxylovaný alkohol | 13,6 | 10 až 20 |
| Hexylenglykol | 27,3 | 20 až 30 |
| Parfém Pevné látky | 0,4 | 0 až 1,0 |
| Enzym proteása . | 0,4 | 0 až 1,0 |
| Citran trisodný, bezvodý | 4,3 | 3 až 6 |
| Perborát sodný (PB-1) | 3,4 | 2 až. 7 |
| Nonanoyloxybenžensulfonan sodný (NOBS) | 8,0 | 2 až 12 |
| Uhličitan sodný | 13,9 | 5 až 2 0 |
| Diethyltriaminpentaoctová kyselina (DTPA) | 0,9 | 0 až 1,5 |
| Zjasňovací prostředek | 0,4 | 0 až 0,6 |
| Potlačovač pěnění | OJ | 0 až 0,3 |
| Nevýznamné složky | Do celkového vyčíslení |
C12 áž Ci6 methylem rozvětvený alkylsulfát, sodná sůl, připravená dle výše uvedeného návodu
Příklad 3
Kapalina pro ruční mytí nádobí má následující složení.
| Složka | Hmotn. % | Rozsah (hmotn..%) |
| Rozvětvený AS* | 13,0 | 5 až 15 |
| C ,2 až C, 3 alky léthoxy sulfát amonný | 15,0 | 10 až 35 |
| Aminoxid kokosového ořechu | 2,6 | 2 až 5 |
| Betaiň**/Tetronic 704® | 0,87 až 0,10 | 0 až 2 (směs) |
| Ethoxylovaný alkohol CgEj i | 5,0 | 2 až 10 |
• v • · * • ··♦*
| Xylensulfonan amonný ' | 4,0 | 1 až 6 |
| Ethanol | 4,0 | 0 až 7 |
| Citran amonný | 0,06 | 0 áž 1,0 |
| Chlorid horečnatý | 3,3 | 0 až 4,0 |
| Chlorid vápenatý | 2,5 | 0 až 4,0 |
| Síran amonný | 0,08 | 0 až. 4,0 |
| Peroxid vodíku | 200 ppm | 0 až 300 ppm |
| Parfém | 0,18 | 0 až 0,5 |
| Přoteasa Maxaíase® | 0,50 | 0 až 1,0 |
| Voda a minoritní složky | Do celkového vyčíslení |
Ci2až Ci4 methylem rozvětvený alkylsulfát, triethanolamonná sůl, připravená dle výše uvedeného návodu
Alkylbetam z kokosu
Claims (5)
- PATENŤOVÉ NÁROKY1. Způsob přípravy ve středu řetězce až blízko středu řetězce, rozvětvených alkoholů, vyznačující s e t í m, že-zahrnuje krokya) dimerizace balkenů vzorce RCT1-CH2 a ROEE^CEE za tvorby alkenů vzorceR-CH2CH2“Č-R' a
- 2h2R· CH2CH2-C-R kde ve výše uvedených vzorcích R a R' jsou stejné nebo různé C3 až C7 nerozvětvené alkylové substituenty; následované buďb) ižomerizací alkenů z kroku a) a následnou reakcí uvedených ísomerizovaných alkenů s CO/EE za podmínek oxó-proeesu; nebo přímo reakcí alkenů z kroku a) s CO/H2 ža podmínek oxoprocesu;ac) získáním žádaných rozvětvených alkoholů-vzorce ch3RCH2CH2ÓH-R'-CH2OH a CH3 hoch2—R-CH2CH2-CH-R'2. Způsob přípravy povrchově aktivních sulfátů s rozvětvenými alkyly, v y z n a č u j í c í s e t í in, že se sulfatují alkoholy, připravené podle nároku 1.
- 3. Způsob přípravy ethoxysulfaíů srozvětvenými alkyly, vyznačuj ící se t í rii, že zahrnuje nejprve ethoxylaci á poté sulfataci alkoholů připravených podle nároku 1.
- 4. Způsob přípravy povrchově aktivních karboxylatů s rozvětvenými řetězci, vyznačující se t í m, že se oxidují alkoholy připravené podle nároku 1 nebo jejich aldehydické meziprodukty.I · «44 • «44 * ·
- 5. Způsob přípravy povrchově aktivního tauratu s rozvětveným acylem, povrchově aktivního isethionátů s rozvětveným acylem, povrchově aktivního sarkosinatu s rozvětveným acylem nebo povrchově aktivního N-methylglukaminu s rozvětveným řetězcem nebo podobně, vyznačující se t í m, žese jako zdrojový materiál použijí rozvětvené karboxyláty připravené podle nároku 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1552196P | 1996-04-16 | 1996-04-16 |
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|---|---|
| CZ334598A3 true CZ334598A3 (cs) | 1999-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CZ983345A CZ334598A3 (cs) | 1996-04-16 | 1997-04-16 | Výroba rozvětvených povrchově aktivních látek |
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| Country | Link |
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| US (4) | US6320080B2 (cs) |
| EP (1) | EP0900181B1 (cs) |
| JP (1) | JPH11507957A (cs) |
| KR (1) | KR100307426B1 (cs) |
| CN (2) | CN1106366C (cs) |
| AT (1) | ATE220389T1 (cs) |
| AU (1) | AU2991097A (cs) |
| BR (1) | BR9708678A (cs) |
| CA (1) | CA2252435C (cs) |
| CZ (1) | CZ334598A3 (cs) |
| DE (1) | DE69713887T2 (cs) |
| ES (1) | ES2179342T3 (cs) |
| MA (2) | MA24136A1 (cs) |
| MX (1) | MX219947B (cs) |
| TR (1) | TR199802077T2 (cs) |
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| ZA (1) | ZA973246B (cs) |
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-
1997
- 1997-04-14 MA MA24549A patent/MA24136A1/fr unknown
- 1997-04-14 MA MA24550A patent/MA24137A1/fr unknown
- 1997-04-16 KR KR19980708437A patent/KR100307426B1/ko not_active Expired - Fee Related
- 1997-04-16 AU AU29910/97A patent/AU2991097A/en not_active Abandoned
- 1997-04-16 ZA ZA9703246A patent/ZA973246B/xx unknown
- 1997-04-16 JP JP9537387A patent/JPH11507957A/ja active Pending
- 1997-04-16 CN CN97195560A patent/CN1106366C/zh not_active Expired - Fee Related
- 1997-04-16 CA CA002252435A patent/CA2252435C/en not_active Expired - Fee Related
- 1997-04-16 DE DE69713887T patent/DE69713887T2/de not_active Expired - Fee Related
- 1997-04-16 ES ES97924504T patent/ES2179342T3/es not_active Expired - Lifetime
- 1997-04-16 AT AT97924504T patent/ATE220389T1/de not_active IP Right Cessation
- 1997-04-16 EP EP97924504A patent/EP0900181B1/en not_active Revoked
- 1997-04-16 BR BR9708678A patent/BR9708678A/pt not_active Application Discontinuation
- 1997-04-16 CZ CZ983345A patent/CZ334598A3/cs unknown
- 1997-04-16 CN CNB011244135A patent/CN1318397C/zh not_active Expired - Fee Related
- 1997-04-16 TR TR1998/02077T patent/TR199802077T2/xx unknown
- 1997-04-16 WO PCT/US1997/006485 patent/WO1997038957A1/en not_active Application Discontinuation
-
1998
- 1998-10-13 US US09/170,694 patent/US6320080B2/en not_active Expired - Lifetime
- 1998-10-13 US US09/170,185 patent/US6015781A/en not_active Expired - Lifetime
- 1998-10-15 MX MX9808555A patent/MX219947B/es unknown
-
1999
- 1999-11-04 US US09/433,853 patent/US6133222A/en not_active Expired - Lifetime
-
2000
- 2000-06-27 US US09/604,233 patent/US6326348B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| MA24137A1 (fr) | 1997-12-31 |
| US6326348B1 (en) | 2001-12-04 |
| US20010034461A1 (en) | 2001-10-25 |
| ES2179342T3 (es) | 2003-01-16 |
| CA2252435A1 (en) | 1997-10-23 |
| JPH11507957A (ja) | 1999-07-13 |
| CN1106366C (zh) | 2003-04-23 |
| DE69713887D1 (de) | 2002-08-14 |
| CA2252435C (en) | 2004-03-23 |
| CN1358710A (zh) | 2002-07-17 |
| US6320080B2 (en) | 2001-11-20 |
| TR199802077T2 (xx) | 1999-01-18 |
| MX9808555A (cs) | 1999-02-28 |
| WO1997038957A1 (en) | 1997-10-23 |
| ATE220389T1 (de) | 2002-07-15 |
| CN1222133A (zh) | 1999-07-07 |
| EP0900181A1 (en) | 1999-03-10 |
| US6015781A (en) | 2000-01-18 |
| EP0900181B1 (en) | 2002-07-10 |
| CN1318397C (zh) | 2007-05-30 |
| MA24136A1 (fr) | 1997-12-31 |
| KR20000005563A (ko) | 2000-01-25 |
| ZA973246B (en) | 1997-11-14 |
| KR100307426B1 (ko) | 2001-11-30 |
| AU2991097A (en) | 1997-11-07 |
| MX219947B (cs) | 2004-04-16 |
| BR9708678A (pt) | 1999-08-03 |
| DE69713887T2 (de) | 2003-02-27 |
| US6133222A (en) | 2000-10-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PD00 | Pending as of 2000-06-30 in czech republic |