WO2001029112A1 - Process for the production of zwitterionic polyamines - Google Patents
Process for the production of zwitterionic polyamines Download PDFInfo
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- WO2001029112A1 WO2001029112A1 PCT/EP2000/009923 EP0009923W WO0129112A1 WO 2001029112 A1 WO2001029112 A1 WO 2001029112A1 EP 0009923 W EP0009923 W EP 0009923W WO 0129112 A1 WO0129112 A1 WO 0129112A1
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- Prior art keywords
- alkoxylated
- sulfur trioxide
- quatemized
- polyamines
- sulfation
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/02—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor of the thin-film type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
Definitions
- the present invention relates to a process for the production of zwitterionic polyamines by sulfation of alkoxylated and quatemized polyamines and subsequent neutralization.
- EP-A-0,111,976 and EP-A-0, 112, 592 relate to zwitterionic polyamines which are for example obtained by alkoxylation of polyal- kyleneamines such as triethylenea ine or tetraethylenepentamine, quaternization of the alkoxylated polyalkyleneamines and subsequent sulfation with chlorosulfonic acid in an inert solvent.
- the inert solvent and hydrogen chloride formed during the reaction must be removed from the reaction product.
- zwit- terionic monoamines are prepared by reacting 1 mole of the reaction product of an amine having the formula RNH2 with 5 to 50 moles of ethylene oxide, subsequently with 0.5 to 1.0 mole of a quaternizing agent such as dimethyl sulfate or alkyl halides and then reacting the resulting quatemized polyethoxylated monoamine with 0.1 to 2.0 mole of a sulfating agent selected from the group consisting of chlorosulfonic acid, sulfur trioxide, sulfamic acid and sulfuric acid oleum.
- a quaternizing agent such as dimethyl sulfate or alkyl halides
- U.S. Patent 4,285,881 relates to a method for the removal of dioxane from ether sulfa- tes by treating dioxane containing mixtures with water vapor at temperatures of 25 - 150°C in a falling film stripper. According to other methods dioxane is removed from polyethylene glycolether sulfates under reduced pressure, azeotropically or with zeoli- thes, cf .
- the above abject is achieved with a process for the production of zwitterionic polyamines by sulfation of alkoxylated and quaterni- zed amines and subsequent neutralization when continuously sulfating an alkoxylated and quatemized polyamine having at least two tertiary or quaternary amine nitrogen atoms in the molecule and containing at least one quatemized nitrogen atom, in the form of a film having a thickness of from 100 ⁇ m to 4 mm in the absence of a solvent with a sulfur trioxide-containing inert gas at a temperature of up to 90°C.
- the process is preferably carried out in a falling film reactor with a sulfur trioxide/air or nitro mixture.
- the alkoxylated and quatemized polyamine contains 2 to 10 nitrogen atoms and at least 20 alkylene oxide unts per nitro- gen atom and has a degree of quaternization of at least 80%.
- alkoxylated and quate ized polyamines having at least two tertiary or quaternary amine nitrogen atoms in the molecule and containing at least one quatemized nitrogen atom are sulfated.
- the products which are sulfated are, for example, obtained from polyamines having 2 to 10 nitrogen atoms by alkoxylation and quaternization.
- Polyamines of particular interest are hexamethylenediamine, bis (hexamethylenediamine and polyetherpolyamines .
- the polyetherpolyamines can be linear or branched and contain 2 to 10, preferably 2 to 6 and most preferably 2 to 4 nitrogen atoms and have a molecular weight of from 100 to 800, preferably 120 to 500.
- the polyetherpolyamines can be described by the following formula:
- B is a linear or branched C - to C -alkylene
- D is a linear, branched or cyclic C 5 - to Ci ⁇ -alkylene, C- to Ci 6 -oxaalkylene or C 5 - to C 16 -azaalkylen, m is 0-7, o is 0 or 1 , p is 0-6, with the proviso that m+o+p > 1 up to 9.
- Examples of compounds of the above formula I are hydrogenated cy- anomethylated C3- to C12-diols. These compounds are obtained by reacting first a diol with formaldehyde and hydrogencyanide and subsequently hydrogenating the addition product in the presence of ammonia. This method of producing amines is hereinafter referred to as aminoethylation.
- Compounds so produced are espe- cially 1, 9-diamino-3 , 7-dioxa-nonane, 1, 10-diamino-3, 8-dioxade- cane, 1, 12-diamino-3, 10-dodecane and 1, 14-diamino-3, 12-tetrade- cane.
- Suitable polyalkylene glycols contain preferably 2 to 10 repeating units and are derived from polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetrahydrofurane.
- the polyalkylene glycols may contain the repeating units in statistical distribution or as blocks. Examples of such compounds are
- Further compounds of formula I are hydrogenated cyanoethylated C 2 - to C ⁇ -diols which are obtained by reacting a diol with acrylo- nitrile in a molar ratio of about 1 to 2 in a Michael type addition reaction and hydrogenating the Michael addition product thus obtained in the presence of ammonia.
- This method of producing amines is hereinafter referred to as aminopropylation.
- Examples of such compounds are 1, 10-diamino-4 , 7-dioxa-decane, 1, 10-diamino-5-methyl-4, 7-dioxa-undecane,
- Another group of compounds of formula I are hydrogenated cyanoethylated polyalkylene glycols having 2 to 10 repeating units. These compounds are obtained by reacting a polyalkylene glycol with acrylonitrile according to a Michael addition to acrylo- nitrile in a molar ratio of 1 to 2 and hydrogenating the addition products (aminopropylation) .
- Suitable polyalkylene glycols are specified above.
- Examples of compounds of this group are 1, 13-diamino-4,7, 10-trioxa-tridecane, 1, 13-diamino-5, 8-dimethyl-4 , 7, 10-trioxa-undecane, 1, 16-diamino- ,7,10, 13-tetraoxa-hexadecane,
- Suitable amines of this type are obtained by amination of polyethylene glycol, polypropylene glycol or polytetrahydrofurane containing blockcopolymers containing 7 to 10 ethylene oxide units and 2 to 5 propylene oxide units, i.e. reaction of ammonia with said blockcopolymers under exchange of the OH end groups of the blockcopolymers by NH 2 groups.
- Aminoethylated, aminopropylated or aminated polyalkylene glycols derived from polyethylene glycol and polyethylene glycol reacted at the endgroups with 1-2 moles propylene oxide or butylene oxide or poly- tetrahydrofuran are preferred.
- the preferred total number of alkylene oxide units within these polyalkylene glycols is of from 3 to 9 most preferred from 3 to 6.
- the polyetherpolyamines can have the formula
- B is a linear or branched C 2 - to C 4 -alkylene
- R 2 is -H, Ci- to C 6 -alkyl , H T is — (0-B) ra — N , (0-B) m 0 H
- the polyetherpolyamine of formula II is derived from branched structures which can be obtained from polyols having 3 to 6 hydroxy groups such as glycerol, trimethylolmethane, trimethylo- lethane, trimethylolpropane, pentaerythritol, sorbit and mannit, by alkoxylation with 1 to 4 molecules of ethylene oxide, propylene oxide, butylene oxide or their mixtures per OH group in the polyol and subsequent reaction with ammonia in order to convert the OH groups into NH groups.
- Other methods of producing amines having a spacer of formula IV consist either in aminome- thylation or aminopropylation of the above polyols with 3 to 6 hydroxy groups.
- Examples of such compounds are the aminated reaction products of 1 mole of glycerol with 3 to 7 moles of ethylene oxide, aminated block copolymers obtained by reacting 1 mole of glycerol with 3 moles of propylene oxide and subsequently with 7 moles of ethylene oxide, aminated reaction products of 1 mole of trimethylolpropane with 3 to 7 moles of ethylene oxide, aminated reaction products of block copolymers obtained by reacting 1 mole of trimethylolpropane with 3 moles of propylene oxide and further with 7 moles of ethylene oxide, aminated reaction products of an ethoxylated pentaerythrit containing 4 to 8 ethylene oxide units and aminated reaction products of an alkoxylated pentaerythrit containing blocks of 4 propylene oxide units and 8 ethylene oxide units.
- Of specific interest is an aminated propoxylated trimethylolpropane containing 9 propylene oxide units.
- Preferred polyetherpolyamines of formula II are those obtained from glycerol, trimethylolpropane and pentaerythrit. Especially preferred are those obtained by aminopropylation.
- E is — CH 2 — CH — CH 2 — , — CH 2 — C— CH 2 ,
- T is 0— (CH 2 ) q — N ⁇ OH
- R 1 is H, CH 3 , C 2 H 5 and q is 2 or 3.
- Preferred amines of formula V are the reaction products obtained by aminoethylation of glycerol, trimethylolpropane or penta- erythrit or the aminopropylated reaction products of the said alcohols with the proviso that all OH groups of the polyols are aminoethylated or aminopropylated respectively.
- Suitable polyetherpolyamines may for instance have the following formulae
- D is — CH 2 — CH 2 — CH 2 — CH 2 — , — CH 2 — CH 2 — 0 — CH 2 - CH 2 — ,
- q 2 or 3.
- Preferred polyamines of formula IV are bis (aminoethylated) or bis (aminopropylated) alcohols selected from the group consisting of ethylene glycol, propylene glycol, butanediol-1, 4 , hexane- diol-1,6 and diethylene glycol.
- the polyamines can also be derived from linear or branched hydro- phobic polyamines which may be described by the following formulae
- ⁇ , ⁇ -diamines having a spacer selected from the group consisting of C ⁇ - to C ⁇ 6 -alkylene and C 5 - to Cis-cycloalkylene between the nitrogen atoms .
- polyamines selected from the group consisting of bis (hexamethylene) triamine, N,N' -bis (3-aminopro- pyl) piperazine, N,N' -bis (2-aminoethyl) iperazine and N,N'- bis (3 -aminopropyl) hexamethylenediamine.
- Polyamines contain which a C ⁇ - to Ci 6 ⁇ alkylene group as spacer are for example 1, 8-diaminooctane, 1, 10-diaminodecane and 1,12-diami- nododecane.
- suitable polyamines containing the above spacers of formula V - VIII are dipropylenetriamine, tripropyle- netetramine, bis (hexamethylene) triamine, bis (octamethylene) tria- mine, aminoethylpropylenediamine, aminoethylbutylenediamine, ami- noethylhexamethylenediamine, N,N'-bis (aminoethyl)propylenedia- mine, N,N' -bis (aminoethyl)butylenediamine, N,N' -bis (aminoe- thyl) hexamethylenediamine, N,N' -bis (aminopropyl) ethylendiamine, N,N' -bis (aminopropyl) butylenediamine, N,N' -bis (aminopropyl)buty- lendiamine, N,N' -bis (aminopropyl)
- Polyamines with spacers consisting of a cyclic C5- to C15-alky- lene group are for example 1, 3-cyclohexylenediamine, 4 -methyl -1,3 -eyelohexylenediamine, 2 -methyl- 1, 3 -cyclohexylene- diamine, isophoronediamine and 4, 4' -diamino (biscyclohexy- lene) methane.
- Polyamines which contain other cyclic spacers are, for example, o-, m-, and p-di (aminomethylen) benzene, N,N' -bis (aminoethyl) piperazine, N,N' -bis (aminopropylpiperazine and N-aminopropylpipera- zine.
- Preferred polyamines contain 2 to 6 nitrogen atoms in the molecule.
- examples of such compounds are ethylenediamine, propylene- diamine-1,3, butylenediamine-1, 4 , neopentyldiamine, hexa- methylenediamine-1, 6 , diethylenetriamine, tetraethylenepentamine, 2- (ethylamino) ethylamine, 3- (methylamino)propylamine, 3-(cyclo- hexylamino)propylamine, 3- (2-aminoethyl) aminopropylamine, 2-diethylamino) ethylamine, 3- (dimethylamino)propylamine, dime- thyldipropylentriamine, 4-aminoethyloctane-l, 8-diamine, 3- (diethylamino)propylamine, N;N-diethyl-l , 4-pentanediamine, ami
- Suitable polyamines as starting materials for the production of- zwitterionic polyamines are in addition to the above polyamines condensation products which are obtainable by reacting
- a crosslinker selected from the group consisting of epihalo- hydrins, polyglycidyl ethers with 2 to 4 glycidyl groups, po- lyhalohydrins with 2 to 4 halohydrine groups, dicarboxylic acids, their esters chlorides, amides or anhydrides, diiso- cyanates, urea and melamine, in a ratio (i) : (ii) of from 20 : 1 to 1 : 1 with reference to molar amounts of amino groups in the amines of (i) and molar amounts of reactive groups in the crosslinker of (ii) , resulting in the formation of a crosslinked polyamine having a molecular weight of from 150 to 1,500.
- Suitable amines (i) for the preparation of the condensation products are for example primary Cl- to C22-alkylamines, C7- to C22-aralkylamines, C6- to C22-cycloalkylamines, monohydroxy-C2- to C4-alkylamines, dihydroxy-C2- to C4-alkylamines trihydroxy-C2- to C4-alkylamines, linear or branched C2- to C12-alkylenedia- mines, C8- to C22-aralkylendiamines, C7- to C22-cycloalkylenedia- mines, ⁇ , ⁇ -polyetherdiamines containing 1 to 10 alkoxy units between the nitrogen atoms and linear or branched polyalkylenepoly- amines having 2 to 4 C2- to C12-alkyleneamine units.
- Examples for the above groups of amines are methylamine, ethylamine, propylamine, butylamine, octylamine, 2-ethylhexylamine, benzylamine,
- ethylenediamine 1, 3-diaminopropane, 1, 4-diaminobutane, 1,6-di- aminohexane, 1, 3-diamino-3, 3-dimethylpropane, piperazine, 4, 9-dioxadodecanediamine-l, 12, 4,7, 10-trioxatridecanedia- mine-1,13, 4 , 11-dioxatetradecanediamine-l, 14 , ⁇ , ⁇ -diaminopoly- ethyleneglycole with 2-10 ethyleneglycole-units, ⁇ , ⁇ -diaminopoly- propyleneglycole with 2-10 propyleneglycole-units, ⁇ , ⁇ -diamino- polytetrhaydrofurane with 2-10 oxabutylene-units, Isophoronedi- mine, bis (4-aminocyclohexyl) methane, 1, 3-dia
- Especially preferred amines for the preparation of the condensation products are diethanolamine, bis- (2-hydroxypropyl) amine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 4, 9-dioxadodecanediamine-l, 12, 4, 7, 10-trioxatridecanedi - amine-1,13, diethylenetriamine, dipropylenetriamine, bishexame- thylenetriamine and bis (aminopropyl) piperazine.
- Suitable crosslinkers (ii), which contain at least two functional groups, are for example ⁇ -, ⁇ - or vicinal dichloroalkanes having at least 4 carbon atoms such as 1, 4-dichlorobutane and 1,6-di- chlorohexane .
- Further suitable crosslinkers are glycidyl halides such as epichlorohydrin, bischlorohydrin ethers of polyols, polychlorohydrin ethers of polyols, bischlorohydrin ethers of polyalkylene glycols, chloroformic acid esters, chlorides of dibasic saturated dicarboxylic acids, phosgene and, in particular, halogen-free crosslinkers.
- crosslinkers are epichlorohydrin and bischlorohy- drin ethers of ethylene glycol, polyethylene glycol having 2 to 20 especially 2 to 14 ethylene glycol units, propylene glycols, polypropylene glycols, copolymers of ethylene oxide and propylene oxide, butanediol-1, 4, neopentyl glycol, hexanediol-1, 6, resorci - nol, glycerol, diglycerol and pentaerythritol.
- crosslinkers are trischlorohydrinethers of trimethylolpropane, glycerol and pentaerythrithol and the reaction product 1 mole of pentaerythritol with 4 moles of epichlorohydrin.
- Halogen-free crosslinkers which are at least bifunctional are preferably se ⁇ lected from the group consisting of:
- diepoxides such as hexamethylene diisocyanate
- Diepoxides and poly- epoxide may be obtained from bischlorohydrinethers of alkylene glycols and polyethylene glycols or from tris and tetrachlorohy- drinethers of polyols such as trimethylolpropane and pentaerythritol .
- Suitable halogen-free group (2) crosslinkers are di- basic saturated carboxylic acids, such as C 4 -C ⁇ _ -dicarboxylic acids, and also the salts, diesters and diamides which are derived therefrom.
- acids are succinic acid, adipic acid, terephthalic acid, phthalic acid and ⁇ , ⁇ -dodecanoic acid.
- esters of the dicarboxylic acids which come into consideration are preferably derived from alcohols having from 1 to 4 carbon atoms.
- suitable dicarboxylic acid esters are dimethyl succinate, diethyl succinate, diisopropyl succinate, di- n-propyl succinate, diisobutyl succinate, dimethyl adipate, diethyl adipate and diisopropyl adipate.
- dicarboxylic acid anhydrides examples include phthalic anhydride and succinic anhydride.
- Preferred compounds of group (3) are bisglycidyl ethers of ethylene glycol, polyethylene glycol having 2 to 20 ethylene glycol units, propylene glycol, polypropylene glycol ethers, copolymers of ethylene oxide and propylene oxide, butanediol-1, 4, neopentyl glycol, hexanediol -1, 6 and resorcinol and diisocyanates such as hexamethylene diisocyanate.
- Crosslinked polyamines are obtainable by reacting at least one compound of group (i) with at least one compound of group (ii) .
- the reaction may be carried out in substance, in solution in an inert solvent or in dispersion in an aqueous medium or in an inert solvent.
- Preferred polyamines of this group are those wherein the cross - linked polyamine backbone is obtained by reacting (i) an amine selected from the group consisting of diethanola- mine, bis (2-hydroxypropyl) amine, 1, 3-diaminopropane, 1,4-dia- minobutane, 1, 6-diaminohexane, 4 , 9-dioxadodecanediamine-l, 12 , 4 , 7 , 10-trioxatridecanediamine-l, 13 , diethylenetriamine dipro- pylenetriamine, bis (hexamethylene) triamine and bis (aminopropyl) piperazine with
- a crosslinker selected from the group consisting of epichlorohydrin, bischlorohydrinethers of C2- to C6- alkylene gly- cols, bischlorohydrinethers of polyethylene glycols having 2 to 14 ethylene glycol units, trischlorohydrinether of trimethylolpropane, trischlorohydrinether of glycerol, tetrachlo- rohydrinether of pentaerythritol, bisglycidylether of ethylene glycol, bisglycidylether of polyethylene glycols having 2 to 14 ethylene glycol units, trisglycidylether of trimethylolpropane, tetraglycidylether of pentaerythritol, urea, me- lamine, adipic acid, terephthalic acid, phthalic acid, ⁇ , ⁇ -dodecanoic acid and hexamethylene diisocyanate.
- A means an ethylene oxide unit, a propylene oxide unit, a unit of butylene oxides and a tetrahydrofuran unit, and n is a number of from 1 to 50.
- each molecule of the polyamines contains at least 20, preferably 50 to 200 alkylene oxide units.
- Ethylene oxide and propylene oxide are the preferred al- koxylating agents. If a mixture of alkylene oxides is added to the amino nitrogen then the polymerized alkylene oxides may be present in statistical distribution or as blocks. For example one can add first 10 to 20 of ethylene oxide units per NH group in the polyamines and then add 5 to 10 propylene oxide units or vice versa.
- ethylene oxide alone or a combination of 1-15% propylene oxide or 1-10% butylene oxide with 85-99, 90-99% ethylene oxide respectively are used. If a combination of ethylene oxide and propylene oxide or butylene oxide is used pre- ferably the propylene oxide or butylene oxide is reacted first with the NH and OH-groups of the polyamines and the ethylene oxide is added after that.
- the polyamines are preferably ethoxy- lated.
- the alkoxylated polyamines are quatemized by reacting them with a quaternizing agent.
- Suitable quaternizing agents are for example C ⁇ to C 2 -alkylhalides, C 7 - to C22-aralkyl halides Ci -C 2 -dialkylsulfates or alkylene oxides.
- Examples of quaternizing agents are dimethyl sulfate, diethyl sulfate, methylchloride, ethyl chloride, methyl bromide, ethyl bromide, butyl bromide, hexyl chloride, benzyl chloride, benzyl bromide, ethylene oxide or propylene oxide.
- Dialkylsulfates especially dimethyl sulfate and diethyl sulfate are the most preferred quaternizing agent.
- Up to 100% of the tertiary nitrogen atoms of the polyetherpolyamines may be quatemized.
- the degree of quaternization is, for example, 10 to 100%, preferably at least 80 % and more preferably more than 90 to 100%. In most cases the alkoxylated polyamines are fully quatemized.
- the starting materials for the sulfation step are alkoxylated and quate ized polyamines containing 2 to 10 nitrogen atoms and at least 20 alkylene oxide units per molecule with a degree of qua.- temization of at least 80%. More preferably the alkoxylated and quatemized polyamines contain 2 to 6 nitrogen atoms and 50 to 200 alkylene oxide units per molecule and have a degree of qua- temisation of more than 90%. Most preferred are fully quatemized alkoxylated poyamines as starting materials for the sulfation.
- the above starting materials are sulfated in the absence of a solvent. It is however possible to dilute the alkoxylated and quatemized polyamines with compounds which reduce the viscosity of the said polyamines and which react with sulfur trioxide to products used in detergents for textiles or in cleaning compositions. Such compounds are for example xylene, cumene, alkoxylated alkohols, monoamines or amides.
- the viscosity of alkoxylated, quatemized polyamines is within the range of 20 to 1,500 mPas, most preferably from 40 to 800 mPas (measured in a Brookfield vi - scosimeter at a temperature of 60°C) .
- the alkoxylated, quatemized polyamines are continuously sulfated in the form of a film having a thickness of from 100 ⁇ m to 4 mm, preferably of from 200 ⁇ m to 2 mm with a sulfur trioxide containing inert gas at a temperature of up to 90°C. Air and nitrogen are the most preferred inert gases for the sulfation step.
- 10 sulfating may be carried out with a sulfur trioxide/air mixture which contains 1 to 10% by weight of sulfur trioxide or with a sulfur trioxide/nitrogen mixture containing 1 to 10% by weight of sulfur trioxide.
- the inert gas is preferbably heated to the temperature at which the sulfation is carried out and is then
- the reaction is usually carried aut in a reactor operating according to the falling film principle.
- the sul- tation can be carried out in various types of falling film reac-
- the alkoxylated, quatemized polyamines are for instance introduced at the top of a perpendicular standing reactor and the sulfur trioxide-containing inert gas is introduced at the bottom of the reactor. This means that the sulfation is preferably carried out countercurrently.
- Reaktor of this type are disclosed in
- the alkoxylated quaternary polyamine is introduced at the top of a multitube perpendicular standing 30 reactor and the sulfortrioxide containing inert gas is introduced also from the top. This means, that the sulfation can also be carried out concurrently in a tubular reactor.
- the reaction temperature is usually in the range of from 20 to 35 80°C, preferably 50 to 70°C.
- the mixture of sulfur trioxide with the inert gas contains, as a rule, per kilogramm of sulfur trioxide 20 to 60 m 3 , preferably 35 to 45 m 3 of the inert gas.
- the molar ratio of hydroxyl end groups of the alkoxylated, quatemized polyamines to sulfur trioxide is for example 1.0 : 0.2 to 40 1.0 : 1.2.
- the amount of sulfur trioxide necessary for sulfation can be controlled by measuring the acid number of the reaction product. If the sulfation of the alkoxylated, quatemized polyamines is 45 not complete in the first pass the reaction product can then be transferred to an other reactor in which an afterreaction is carried out at a temperature within the range given above. The afterreaction can be carried out at a temperature which is higher or lower than the reaction temperature. It is preferred to introduce the sulfation product obtained in the first pass into at least one other falling film reactor for af terreaction. The af - terreaction can be continuously carried out in a reactor operating according to the falling film principle or discontinuously in a stirred vessel.
- the weight average molecular weight Mw of the zwitterionic poly- amines is up to 9,000, preferably from 1,500 to 7,500 and more preferably from 2,000 to 7,000.
- the zwitterionic polyetherpolyamines are soluble or at least easily dispersible in water. They are net anionic, i.e. the average number of anionic charges (S03H groups) exceeds the average number of cationic charges resulting from quatemized amine groups by a factor of, for example, more than 1.2, more preferably of more than 1.5 and most preferably of more than 1.8.
- the zwitterionic products obtained according to the process of the invention contain less dioxane-1,4 and have additionally a better color number than those zwitterionic products which are produced by prior art methods.
- the sulfated alkoxylated, quatemized polyamines are neutralized with bases such as alkali metal hydroxides, alkaline earth metal hydroxides, ammonia and amines.
- bases such as alkali metal hydroxides, alkaline earth metal hydroxides, ammonia and amines.
- the bases are preferably used in aqueous solution. Suitable bases are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium hydroxide, magnesium hydroxide, orpholine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine and dicyclohexy- lamine.
- the zwitterionic polyamines are used as additives in laundry detergent compositions which provide enhanced hydrophilic soil, in- ter alia, clay, removal benefits. They can also be used in cleaning agents, cosmetic and pharmaceutical preparations and in the photo industry.
- Example 1 The degree of quaternization and of sulfation was determined by IH-NMR. The amine number was determined by amine titration according to DIN 16 945. The color number was measured according to DIN 4630. Example 1
- reaction mixture contained 750 ppm of dioxane and had a color number according to Gardner (measured in 50% strength by weight solution) of 1.4.
- the reaction product contained 1.5%
- the sulfated alkoxylated, quate ized diamine obtained in the bottom of the reactor was collected and neutralized batchwise by feeding 750 g of the sulfated product into a mixture of 45 ml of a 25% strength by weight aqueous solution of sodium hydroxide and 700 ml of water while keeping the reaction mixture at a temperature of 30°C.
- the pH of the reaction mixture was then adju- sted to 10 by further addition of an aqueous sodium hydroxide solution.
- the reaction mixture contained 575 ppm of dioxane and had a color number according to Gardner (measured in 50% strength by weight aqueous solution) of 1.0.
- the reaction product contained 2.3% by weight of starting material which had not been sulfa - ted.
- the condensation product which was obtained by condensing 2 moles of 4 , 7-dioxadodecanediamine and 1 mole of epichlorohydrin was ethoxylated with 120 moles of ethylene oxide.
- the ethoxylated condensation product was then fully quatemized with dimethyl sulfate.
- the ethoxylated, quatemized condensation product thus obtained was then continuously sulfated with a sulfur trioxide/ nitrogen mixture containing 6.6 % by volume of sulfur trioxide in the falling film reactor described in Example 1 at a temperature of 60°C.
- 700 g/h of the alkoxylated, quatemized condensation product were heated to 48°C and introduced into the top of the reactor and moved in the form of a film having an average thickness of 1.6 mm downwards and were continuously and concurrently contacted with the sulfur trioxide/nitrogen mixture having a temperature of 60°C (48 g/h sulfur trioxide and 190 1/h of nitrogen) .
- the reaction proceeded at a temperature of 60°C.
- the sulfation ratio of the OH groups of in the alkoxylated, quatemized product to sulfur trioxide was 1 : 0.95.
- the amount of sulfur trioxide which was fed into the reactor was controlled by the acid number of the sulfated product obtained in the bottom of the reactor. The acid number was 50.
- the sulfated alkoxylated, quatemized condensation product obtained in the bottom of the reactor was collected and neutralized batchwise by feeding 750 g of the sulfated product into a mixture of 45 ml of a 25% strength by weight aqueous solution of sodium hydroxide and 700 ml of water while keeping the reaction mixture at a temperature of 30°C.
- the pH of the reaction mixture was then adjusted to 10 by further addition of an aqueous sodium hydroxide solution.
- the reaction mixture contained about 600 ppm of dioxane and had a color number according to Gardner (measured in 50% strength by weight aqueous solution) of 1.6.
- the reaction product contained 2.7% by weight of starting material which had not been sulfated.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0014844-0A BR0014844A (pt) | 1999-10-19 | 2000-10-10 | Processo para produção de poliaminas zwitteriÈnicas por sulfatação de aminas alcoxiladas e quaternizadas e subsequente neutralização |
AU11355/01A AU1135501A (en) | 1999-10-19 | 2000-10-10 | Process for the production of zwitterionic polyamines |
JP2001531904A JP2003512389A (ja) | 1999-10-19 | 2000-10-10 | 両性イオン性ポリアミンの製造方法 |
KR1020027004894A KR20020047243A (ko) | 1999-10-19 | 2000-10-10 | 양쪽성 이온 폴리아민의 제조 방법 |
CA002384138A CA2384138A1 (en) | 1999-10-19 | 2000-10-10 | Process for the production of zwitterionic polyamines |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16021299P | 1999-10-19 | 1999-10-19 | |
US60/160,212 | 1999-10-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001029112A1 true WO2001029112A1 (en) | 2001-04-26 |
Family
ID=22575969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/009923 WO2001029112A1 (en) | 1999-10-19 | 2000-10-10 | Process for the production of zwitterionic polyamines |
Country Status (7)
Country | Link |
---|---|
JP (1) | JP2003512389A (ja) |
KR (1) | KR20020047243A (ja) |
CN (1) | CN1379793A (ja) |
AU (1) | AU1135501A (ja) |
BR (1) | BR0014844A (ja) |
CA (1) | CA2384138A1 (ja) |
WO (1) | WO2001029112A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001062882A2 (en) * | 2000-02-23 | 2001-08-30 | The Procter & Gamble Company | Granular laundry detergent compositions comprising zwitterionic polyamines |
US7550621B2 (en) | 2004-03-19 | 2009-06-23 | The Procter & Gamble Company | Process of sulfating select polymers |
US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
WO2021239547A1 (en) | 2020-05-29 | 2021-12-02 | Basf Se | Amphoterically-modified oligopropyleneimine ethoxylates for improved stain removal of laundry detergents |
WO2023094275A1 (en) | 2021-11-29 | 2023-06-01 | Basf Se | Amphoterically-modified trialkylene tetramine ethoxylates for improved stain removal of laundry detergents |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100975898B1 (ko) * | 2008-01-21 | 2010-08-13 | 경희대학교 산학협력단 | 에테르기가 치환된 이미다졸륨계 양쪽성 이온 및 그를포함하는 리튬 이차전지용 전해질 조성물 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1445997A (en) * | 1973-11-06 | 1976-08-11 | Unilever Ltd | Process for sulphating ethoxylated secondary alcohols |
EP0111976A2 (en) * | 1982-12-23 | 1984-06-27 | THE PROCTER & GAMBLE COMPANY | Zwitterionic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions |
DE4137221A1 (de) * | 1991-11-13 | 1993-05-19 | Henkel Kgaa | Verfahren zur herstellung sulfatierter fettsaeurealkanolamide |
DE19714043A1 (de) * | 1997-04-05 | 1998-10-08 | Henkel Kgaa | Verwendung von Glycerinsulfaten als Viskositätsregulatoren für konzentrierte wäßrige Alkyl(ether)sulfatpasten |
US5911958A (en) * | 1995-03-28 | 1999-06-15 | Dahl; Birger | Multitube falling film reactor for the continuous manufacturing of sulfonated and/or sulfated compounds |
-
2000
- 2000-10-10 AU AU11355/01A patent/AU1135501A/en not_active Abandoned
- 2000-10-10 JP JP2001531904A patent/JP2003512389A/ja not_active Withdrawn
- 2000-10-10 KR KR1020027004894A patent/KR20020047243A/ko not_active Application Discontinuation
- 2000-10-10 CN CN00814489A patent/CN1379793A/zh active Pending
- 2000-10-10 WO PCT/EP2000/009923 patent/WO2001029112A1/en not_active Application Discontinuation
- 2000-10-10 BR BR0014844-0A patent/BR0014844A/pt not_active Application Discontinuation
- 2000-10-10 CA CA002384138A patent/CA2384138A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1445997A (en) * | 1973-11-06 | 1976-08-11 | Unilever Ltd | Process for sulphating ethoxylated secondary alcohols |
EP0111976A2 (en) * | 1982-12-23 | 1984-06-27 | THE PROCTER & GAMBLE COMPANY | Zwitterionic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions |
DE4137221A1 (de) * | 1991-11-13 | 1993-05-19 | Henkel Kgaa | Verfahren zur herstellung sulfatierter fettsaeurealkanolamide |
US5911958A (en) * | 1995-03-28 | 1999-06-15 | Dahl; Birger | Multitube falling film reactor for the continuous manufacturing of sulfonated and/or sulfated compounds |
DE19714043A1 (de) * | 1997-04-05 | 1998-10-08 | Henkel Kgaa | Verwendung von Glycerinsulfaten als Viskositätsregulatoren für konzentrierte wäßrige Alkyl(ether)sulfatpasten |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001062882A2 (en) * | 2000-02-23 | 2001-08-30 | The Procter & Gamble Company | Granular laundry detergent compositions comprising zwitterionic polyamines |
WO2001062882A3 (en) * | 2000-02-23 | 2002-03-07 | Procter & Gamble | Granular laundry detergent compositions comprising zwitterionic polyamines |
US7550621B2 (en) | 2004-03-19 | 2009-06-23 | The Procter & Gamble Company | Process of sulfating select polymers |
US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
WO2021239547A1 (en) | 2020-05-29 | 2021-12-02 | Basf Se | Amphoterically-modified oligopropyleneimine ethoxylates for improved stain removal of laundry detergents |
WO2023094275A1 (en) | 2021-11-29 | 2023-06-01 | Basf Se | Amphoterically-modified trialkylene tetramine ethoxylates for improved stain removal of laundry detergents |
Also Published As
Publication number | Publication date |
---|---|
CA2384138A1 (en) | 2001-04-26 |
AU1135501A (en) | 2001-04-30 |
KR20020047243A (ko) | 2002-06-21 |
CN1379793A (zh) | 2002-11-13 |
JP2003512389A (ja) | 2003-04-02 |
BR0014844A (pt) | 2002-06-11 |
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