CA1050384A - Surfactant-containing aluminosilicates and process - Google Patents
Surfactant-containing aluminosilicates and processInfo
- Publication number
- CA1050384A CA1050384A CA208,785A CA208785A CA1050384A CA 1050384 A CA1050384 A CA 1050384A CA 208785 A CA208785 A CA 208785A CA 1050384 A CA1050384 A CA 1050384A
- Authority
- CA
- Canada
- Prior art keywords
- water
- aluminosilicates
- mols
- sio2
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Detergent Compositions (AREA)
Abstract
ABSTRACT
This invention relates to cation-exchanging, water-insoluble aluminosilicates containing bound water and an ionic surface-active compound resistant to water hardness formers and having, for every mol of Al2O3, from 0.7 to 1.5 mols Cat2/nO, where Cat is a cation having the valence n, and from 0.8 to 6 mols SiO2, and being produced by the precipita-tion of said aluminosilicate in an aqueous solution, wherein said reaction is conducted in the presence of an aqueous solution of said ionic surface-active compound, and optional subsequent crystallization; as well as a process for its preparation and a process for the sequestration of water hardness cations employing said aluminosilicates.
-A-
This invention relates to cation-exchanging, water-insoluble aluminosilicates containing bound water and an ionic surface-active compound resistant to water hardness formers and having, for every mol of Al2O3, from 0.7 to 1.5 mols Cat2/nO, where Cat is a cation having the valence n, and from 0.8 to 6 mols SiO2, and being produced by the precipita-tion of said aluminosilicate in an aqueous solution, wherein said reaction is conducted in the presence of an aqueous solution of said ionic surface-active compound, and optional subsequent crystallization; as well as a process for its preparation and a process for the sequestration of water hardness cations employing said aluminosilicates.
-A-
Description
10~389~
Alumino~ilicat0~ containing catlon~ capable of exchaneing w~ich po~es~ the capacity o~ ~eque~tering ions caus~ng ~te:r h~rd~e~ are kno~n. Such ~ubstance~ can be easily o~ta1nedg for example, by reaction of water soluble ~illcate~ with ~ater~oluble alu~nates in the presence of water .
For thi~ purpose, aqueous ~olutlon~ of th0 ~tarting materials can be mixed ~ith each other or ~hen one componen is presen~ aæ ~olld, it can be cau~ed to react ~ith the oth~r 10 which is pre~ent a~ an ~gu~ous ~olutionO Wh~n both compon-ent~ are in the solid ~tate, they can be mixed in the pre-sence o~ ~ater to obtairl the desired alumir~ o~llicates. Such aluminosilicates c~n be al~o prepared by causing Al(OH)3 or A1203 to react wlth alkal~ met~l .ili~ate ~olutions. Proce~s for th~ preparation o~ the~e alumino~ilicatee are de~cribsd, ~or exampl~, ~n copending T~ dian Patent App~ ication Serial No. 197, 628, ~iled April 16~ 1974 o An ob~ect o~ the pre~ent in~ention i~ the obtaining oi cation-exchanging, wat~r-insoluble alumino~ilîcates con-20 taining an iorlic sur~ace acti~e co~ound r~ tant to waterhardrles~ f`orm~rs, having an i ncreas~ cation exchange capa-c~ty and improv~d stab~lity in aqueous ~uspensions.
Another o~ect of the pre~ent inventlon :L8 the develop~ent o~ ¢ation_exchanging, wat~r-in~oluble alumino~
sillcates containing bound water and an ionic aur*ace actiYe compound actlve in the pr~sen~e Or water hardn~ form~re and having ~or ev~ry mol Or A1203, irom 0.7 to 1.5 mol~ of Cat2/nû, wh~re Cat iB a cat~ c~n having the valence n, and from 0.8 to 6 mols of SiO2 31~4 ~ :eurth~r ob~ect c)f the present imrention i~ the development o~ proces~es ~or preparing the above alumino-8iliC~LteB .
A still ~urther ob~ect of the pra~ent inv~ntion iB the improvem~nt in the proce~ oY ~eque~tering water hard-nass cations by ad~ing a ~equ~tering agent to hard water, the improvament consl~t~ o~ employing the abov~ aluminosili-cate~ as said sequestering agent.
These ~nd oth~r ob,~ects o~ the invention ~ill 10 becom~ more apparent a8 the descript1 on ther~o~ proceed~ .
The in~ntion concern~ ne~ cation-~xchanglng alumino~ilicate~ which are capabl~ Or ~eq~e~tering calciu~
ions a~d Nhich contain boundl water. me~ a~uminosilicate~
are ~haracterized by a ~ontent o~ ionic surrace-active com pound~ that are 3.cti~re in the pre~ence of wat~s~ hardnese former~ or r~sista2~t to ths actlon o~ watar hard~e~ rm~r~.
me3e ionic sur~ace-acti-re compouna~ may be called "~ ac-tant~" or "ten~ideæ" hereafter ~or simpllfieation.
The lnvention, ~ere~3re, relate~ to cation-exchang-20 lng, ~ater-~n301ubl~ alumlrlosilicates containiYIg bouIld wat~r and an ionic sur~ace-active compo~nd actlYe in th~ pre~nce o~ ~ater har~es~ former an~ havlne ~or e~ary mol o~
Cat2/nO, where Cat i~ a cation havlng the valence n, and from 0.8 to 6 m~ls of SiO2.
The content o~ sur~actant~ in the ne~r compound~
preferably lies :in the range o~ 0.01% to 50%, e~p~cially 0.1% to 359~, by welght oi~ ~urfact~nt, ba~ed on the mi~ture of sur~actant and anhydrous inorganic acti~re sub~tance (= AS). As ~or the remainder, the new compound~ contain, per mol A1203, pre~erably from 0.7 to 1.5, e~peclally 0.9 l~lS03~9L
to 1.3, mol of Cat2/nO, wher2 Cat repre~ents a cation having the ~alence n~ and ~rom 0.8 to 6. especially ~rom 1.3 to 4~0.5, mols o~ S~02. These aluminosilicate~ contain bound water.
The arnourlt oi bound water will ~ry. Ho~ever, when the alumlno-silicat0s are dried ~or 3 hours at 80C3 und~r a pressure ~f 100 mm of ~e~ the amount o~ bourld water per ~ol A1203 varies ~rom 3 to 10, especially 3.5 to 7.~, mols o~ H~0. The calcium sequestering power of l;hese cs)mpounds pre~erably l~es in the range of from 50 to 200, e~peclally ~rom 80 to 160 mg 10 Cao/gm AS.
The pr~ferred cation i8 sod~um. However, ~odium call be replaced wlth hydrogen, lithium, pota~3ium, ammonium, or magne~ m9 a~ well as with the cations of water-soluble organic bases, ~or example, those o~ primar~r, secondary or tertiary alk~lamines o~r alkylolar~ es having at the most, two carbon atoms p~r alkyl group9 or at the mo~t~ thr~3~ car-bon atom~ per alkylol group.
The ne~r compounas are desi~nated as "alun~nosili-cates" to simpli~y the following discu~sion. me pre~eren-20 tially u~ed compound~ are the so~ium alumino~illcates. Alldata concerni~g thel.r properties, I;h~ir preparation9 and their applicatiorl s,re logically ~alid for the other claim~d compounds .
me new compour~ds di~r from the kno~n on~s by an increased cation exchange capa ity. In additio~, ~queou~
~u~pensions of the compow~d~ are more stab~ e than tho~e o~
the correspond~ng aluminosilicate~ that do not contain any surf`actants. Becau~e of thls property, the compound~ may be employed in the textile washing proces~ ~here the ~ormation 30 o~ ~ediments on the wa~hed textile~ is to be avoided.
3l534 In addition, the invention concer~ a proce~s for the m~nufacture of the new comp:7und~ by the reaction of water-soluble alumlnate~ ~ith water-soluble silicates ln the pre~ence o~ water. The proce~s i~ characterixed in that it is carri~d out in the presence of` arlionic, cationic, or zwitterionic ~ ace-activ~ compoundæ active in the presence o~ water hardr~ess formers.
More particularly, there~ore, the proce~ o~ the invention relate~ to the proce~æ ~or the preparat~on o~
10 aluninosilicate~ by reacting water soluble aluminate~ with water ~oluble 3illcates in the pre~ence of water and reco~r-ing water-insoluble alumino~ilicatesg the improvement consist-ing o~ conducting said reaction i~ the pre~ence oi an aques:~u~
æolu~ion of an ionic s~fa,c~-active compolmd acti~e in the pre~enc~ Or water hardnes~ for~er~.
A praferred process ~or the man~cture o~ the new alumino~ilicates is their pre~ipit~tion by mixi~
aqueou~ aluminate and silicate ~olutions where the ~ur~aetants ~re pre~er~t during the precipitatlon. It has proven advanta~
20 geous to ~tart with the ~u~actant-containing ~ilieate solu-tion and then to admix the alun~inate solution.
me formation of the wat~r~ soluble alumlno~
cates ~n the pre~ence o~ the ab~ -clted ~urfactant~ mak~
it possible ~o slow do~n ~r prevent the cry~allization o~
the aluminosilica~e~ which are fir~t precipitatqd in an X-ray amorphous ~tate and thu~, to keep the particle ~ize o~
the aluminosilicates Yery ~mall. Thi~ particle ~iz~ s mostly below 30~a ~rhereby the maximum o~ the di~trl~ution curve of the particle 8'LZe i9 considerably low~r ~ f or 30 example, in the r~e of 3 to 8,~, but can also decraase to ~ ~5~D3 ~ ~
thc r~nge of true collo~ds. Hence, the ~uspen~lon~ of these X-ray amorphous products obt~ined during the precipi~
tation are more ~table than the ~luspension~ prepar~d in the absence of sur~actants.
me concentration o~ the ~usp~n~ions according to the inventlon pre~erably li0s in the range of ~rom 2~ to 50%, eæpecially ~rom 5% to 35%, by weight of sur~actant-co~taining a~uminosilicate. The abo~e concentration dat~
re~er to the proau~t which has been dried at 80C for 3 hours under a pre~sure o~ 100 mm Hg. Thi~ product, however~ still c~ntains som~ bound water as indicated above.
I~ so desired, the alum~no~llicate susp~n~ions thus prepared can be concentrated by remo~al o~ part of the mother llquor. For mahy purposes o~ application~ the su~st$~
tution of ~ater ~or the mother li~uor i8 advantageouæ.
Finally, the new aluminum slllcates c~n b~ totally ~reed from the mother liquor and converted to dry pswder~ by dr~ing at temperatures Or ~ro~ 20C to 150C. A~t~r ~he pr~cip~-ta~ed products have thus been dried~ they stil~ ~ontain bound water in the order oP 3 to 10 mols per mol A1203.
m is can be completely re~o~ed only by heating to 800C
for one hour whereby, o~ cour~e,~he organic component~ are totally destroyed. The products thus tr~ated are here desig-nated as "anhydrous inorgan~c acti~e substances" (A~). The values ~uoted w~thin the ~ramework of the Example~ ~or the calcium ~e~uestlar~n~ power are calculat~d on th~ ba~s o~
this anhydrous actlve substanc~ as mg CaO/gm AS.
During the preclpitation, the ~ur~actantæ are incorporated lnto the X-r~y amorphous alumino~ilicate bein~
~orm~d and are more or le~s slowly released, depending upon the nature of the ~urfactant, when the~e alum~nosll~cat0~
are introduced into water ~ree ~rom ~ ctants. Th~refore, ~ t i~; advantageous that ~or the pur~f:~cation Or the precip~ta-ted crude products, aqueous solutions o~ the incorporated sur~actant are utilized ~or washing out the mother liquor.
"Ionic ~ actant~ res~stant to the acti~n of water h~rndes~ ~ormer~" within the meaning o~ the inventlon are anionic, cationic, or z~ritterionic water~oluble organ~c ~u~ace-act~ve compoun~ whlch e~n wh~n u~ed in ~11 con-centration~ and in the pre~ence of soluble salt~ caus~ng hardness, appreciably reduce the ~urfac~ tension ~nd which in their molecule contain an aliphatlc hydrocarbon re~i~ue ha~ng 8 tc) 26, pre:Eerabl~ 10 to 22, especlally 10 to 18, carbon atomsa or an alkylaromatic residue h~ving 6 to 18g pre~erably 8 to 16 aliphatic ~arbon atoms, a~d a~ ~i~nic and/or cationic group imparting solubility i~n water.
Zwitterionic sur:l~actants are ~ actants ha~ g molecules which contain anionic and cationlc group~ 5imUlta~ aOllSly.
me anionic ~urfactants comprise tho~e o~ the ~ulfonate, ~ ate, phosphonate ,, arld pho~phate types . In addition, compounds that are res~t~nt t~ the action of water hardness formers are also to be ~ow~d among the synthetic sur~ctEInts of the carboxylate type.
actants o~ the sul~ona~e type which are u~e~ul in the production o~ the product~ o:E the in~ention are alkyl-benzenesul~onates (C9_15 alkyls) or mixture~ o~ alkenesul-~onates and hydroxyalkanesul~onates, as ~11 a3 alk~nedisul-~onates, ~hich are prepar~d, for exampl~, by sul~onating monoolefin~ having terminal ~r non-terminal double bond~
u~ing gaseous sul~ur trioxide, ~ollowed by alkaline or 1~ 5~3U3~
acidic hydrolysiæ oi the sulfonation product~. Other ~uitable alXanesul~onate~ are the onesobtainable by the æulfochlorin-ation or ~ul~oxldation of alkane~, followed by hydrolys~3 or neutralization, or are obtainable by the additio~ of alkali metal bi~ul~ites to olefin~ Additional u~abl~ surfactants o~ the ~ul~on~t~ type are the ester~ o~ ulfo-~atty acid~, for example, the a-~ulfo acids derived ~rom hy~rogenated methyl or ethyl eæters of the ~atty acids derived from coconut oil, palm-kernel oil, or tallow.
Further suitable surfactants o~ the sul~onate type are the fatty acld ~steræ or amide~ of lower hydroxyalkane-sul~onic acids or amino-alkanesulfonic acids. Also u~able are the esters oi higher ~atty alcohols ~ith lo~er ~ul~o-carboxylic acids, ~uch as, for e~a~ple, sulfoacetlc acld, sulfos~cinic acid~ sulfobenzoic acid, sulfosalicyli~ acid, and ~ulfophthalic acid.
Suitable sur~actant~ of the sul~ate typ~ are the monoester~ of ~ulfuric acid ~ith primary higher fatty al~o-hols (~`or example, oleyl alcohol or primary alcohol~ deri~ed
Alumino~ilicat0~ containing catlon~ capable of exchaneing w~ich po~es~ the capacity o~ ~eque~tering ions caus~ng ~te:r h~rd~e~ are kno~n. Such ~ubstance~ can be easily o~ta1nedg for example, by reaction of water soluble ~illcate~ with ~ater~oluble alu~nates in the presence of water .
For thi~ purpose, aqueous ~olutlon~ of th0 ~tarting materials can be mixed ~ith each other or ~hen one componen is presen~ aæ ~olld, it can be cau~ed to react ~ith the oth~r 10 which is pre~ent a~ an ~gu~ous ~olutionO Wh~n both compon-ent~ are in the solid ~tate, they can be mixed in the pre-sence o~ ~ater to obtairl the desired alumir~ o~llicates. Such aluminosilicates c~n be al~o prepared by causing Al(OH)3 or A1203 to react wlth alkal~ met~l .ili~ate ~olutions. Proce~s for th~ preparation o~ the~e alumino~ilicatee are de~cribsd, ~or exampl~, ~n copending T~ dian Patent App~ ication Serial No. 197, 628, ~iled April 16~ 1974 o An ob~ect o~ the pre~ent in~ention i~ the obtaining oi cation-exchanging, wat~r-insoluble alumino~ilîcates con-20 taining an iorlic sur~ace acti~e co~ound r~ tant to waterhardrles~ f`orm~rs, having an i ncreas~ cation exchange capa-c~ty and improv~d stab~lity in aqueous ~uspensions.
Another o~ect of the pre~ent inventlon :L8 the develop~ent o~ ¢ation_exchanging, wat~r-in~oluble alumino~
sillcates containing bound water and an ionic aur*ace actiYe compound actlve in the pr~sen~e Or water hardn~ form~re and having ~or ev~ry mol Or A1203, irom 0.7 to 1.5 mol~ of Cat2/nû, wh~re Cat iB a cat~ c~n having the valence n, and from 0.8 to 6 mols of SiO2 31~4 ~ :eurth~r ob~ect c)f the present imrention i~ the development o~ proces~es ~or preparing the above alumino-8iliC~LteB .
A still ~urther ob~ect of the pra~ent inv~ntion iB the improvem~nt in the proce~ oY ~eque~tering water hard-nass cations by ad~ing a ~equ~tering agent to hard water, the improvament consl~t~ o~ employing the abov~ aluminosili-cate~ as said sequestering agent.
These ~nd oth~r ob,~ects o~ the invention ~ill 10 becom~ more apparent a8 the descript1 on ther~o~ proceed~ .
The in~ntion concern~ ne~ cation-~xchanglng alumino~ilicate~ which are capabl~ Or ~eq~e~tering calciu~
ions a~d Nhich contain boundl water. me~ a~uminosilicate~
are ~haracterized by a ~ontent o~ ionic surrace-active com pound~ that are 3.cti~re in the pre~ence of wat~s~ hardnese former~ or r~sista2~t to ths actlon o~ watar hard~e~ rm~r~.
me3e ionic sur~ace-acti-re compouna~ may be called "~ ac-tant~" or "ten~ideæ" hereafter ~or simpllfieation.
The lnvention, ~ere~3re, relate~ to cation-exchang-20 lng, ~ater-~n301ubl~ alumlrlosilicates containiYIg bouIld wat~r and an ionic sur~ace-active compo~nd actlYe in th~ pre~nce o~ ~ater har~es~ former an~ havlne ~or e~ary mol o~
Cat2/nO, where Cat i~ a cation havlng the valence n, and from 0.8 to 6 m~ls of SiO2.
The content o~ sur~actant~ in the ne~r compound~
preferably lies :in the range o~ 0.01% to 50%, e~p~cially 0.1% to 359~, by welght oi~ ~urfact~nt, ba~ed on the mi~ture of sur~actant and anhydrous inorganic acti~re sub~tance (= AS). As ~or the remainder, the new compound~ contain, per mol A1203, pre~erably from 0.7 to 1.5, e~peclally 0.9 l~lS03~9L
to 1.3, mol of Cat2/nO, wher2 Cat repre~ents a cation having the ~alence n~ and ~rom 0.8 to 6. especially ~rom 1.3 to 4~0.5, mols o~ S~02. These aluminosilicate~ contain bound water.
The arnourlt oi bound water will ~ry. Ho~ever, when the alumlno-silicat0s are dried ~or 3 hours at 80C3 und~r a pressure ~f 100 mm of ~e~ the amount o~ bourld water per ~ol A1203 varies ~rom 3 to 10, especially 3.5 to 7.~, mols o~ H~0. The calcium sequestering power of l;hese cs)mpounds pre~erably l~es in the range of from 50 to 200, e~peclally ~rom 80 to 160 mg 10 Cao/gm AS.
The pr~ferred cation i8 sod~um. However, ~odium call be replaced wlth hydrogen, lithium, pota~3ium, ammonium, or magne~ m9 a~ well as with the cations of water-soluble organic bases, ~or example, those o~ primar~r, secondary or tertiary alk~lamines o~r alkylolar~ es having at the most, two carbon atoms p~r alkyl group9 or at the mo~t~ thr~3~ car-bon atom~ per alkylol group.
The ne~r compounas are desi~nated as "alun~nosili-cates" to simpli~y the following discu~sion. me pre~eren-20 tially u~ed compound~ are the so~ium alumino~illcates. Alldata concerni~g thel.r properties, I;h~ir preparation9 and their applicatiorl s,re logically ~alid for the other claim~d compounds .
me new compour~ds di~r from the kno~n on~s by an increased cation exchange capa ity. In additio~, ~queou~
~u~pensions of the compow~d~ are more stab~ e than tho~e o~
the correspond~ng aluminosilicate~ that do not contain any surf`actants. Becau~e of thls property, the compound~ may be employed in the textile washing proces~ ~here the ~ormation 30 o~ ~ediments on the wa~hed textile~ is to be avoided.
3l534 In addition, the invention concer~ a proce~s for the m~nufacture of the new comp:7und~ by the reaction of water-soluble alumlnate~ ~ith water-soluble silicates ln the pre~ence o~ water. The proce~s i~ characterixed in that it is carri~d out in the presence of` arlionic, cationic, or zwitterionic ~ ace-activ~ compoundæ active in the presence o~ water hardr~ess formers.
More particularly, there~ore, the proce~ o~ the invention relate~ to the proce~æ ~or the preparat~on o~
10 aluninosilicate~ by reacting water soluble aluminate~ with water ~oluble 3illcates in the pre~ence of water and reco~r-ing water-insoluble alumino~ilicatesg the improvement consist-ing o~ conducting said reaction i~ the pre~ence oi an aques:~u~
æolu~ion of an ionic s~fa,c~-active compolmd acti~e in the pre~enc~ Or water hardnes~ for~er~.
A praferred process ~or the man~cture o~ the new alumino~ilicates is their pre~ipit~tion by mixi~
aqueou~ aluminate and silicate ~olutions where the ~ur~aetants ~re pre~er~t during the precipitatlon. It has proven advanta~
20 geous to ~tart with the ~u~actant-containing ~ilieate solu-tion and then to admix the alun~inate solution.
me formation of the wat~r~ soluble alumlno~
cates ~n the pre~ence o~ the ab~ -clted ~urfactant~ mak~
it possible ~o slow do~n ~r prevent the cry~allization o~
the aluminosilica~e~ which are fir~t precipitatqd in an X-ray amorphous ~tate and thu~, to keep the particle ~ize o~
the aluminosilicates Yery ~mall. Thi~ particle ~iz~ s mostly below 30~a ~rhereby the maximum o~ the di~trl~ution curve of the particle 8'LZe i9 considerably low~r ~ f or 30 example, in the r~e of 3 to 8,~, but can also decraase to ~ ~5~D3 ~ ~
thc r~nge of true collo~ds. Hence, the ~uspen~lon~ of these X-ray amorphous products obt~ined during the precipi~
tation are more ~table than the ~luspension~ prepar~d in the absence of sur~actants.
me concentration o~ the ~usp~n~ions according to the inventlon pre~erably li0s in the range of ~rom 2~ to 50%, eæpecially ~rom 5% to 35%, by weight of sur~actant-co~taining a~uminosilicate. The abo~e concentration dat~
re~er to the proau~t which has been dried at 80C for 3 hours under a pre~sure o~ 100 mm Hg. Thi~ product, however~ still c~ntains som~ bound water as indicated above.
I~ so desired, the alum~no~llicate susp~n~ions thus prepared can be concentrated by remo~al o~ part of the mother llquor. For mahy purposes o~ application~ the su~st$~
tution of ~ater ~or the mother li~uor i8 advantageouæ.
Finally, the new aluminum slllcates c~n b~ totally ~reed from the mother liquor and converted to dry pswder~ by dr~ing at temperatures Or ~ro~ 20C to 150C. A~t~r ~he pr~cip~-ta~ed products have thus been dried~ they stil~ ~ontain bound water in the order oP 3 to 10 mols per mol A1203.
m is can be completely re~o~ed only by heating to 800C
for one hour whereby, o~ cour~e,~he organic component~ are totally destroyed. The products thus tr~ated are here desig-nated as "anhydrous inorgan~c acti~e substances" (A~). The values ~uoted w~thin the ~ramework of the Example~ ~or the calcium ~e~uestlar~n~ power are calculat~d on th~ ba~s o~
this anhydrous actlve substanc~ as mg CaO/gm AS.
During the preclpitation, the ~ur~actantæ are incorporated lnto the X-r~y amorphous alumino~ilicate bein~
~orm~d and are more or le~s slowly released, depending upon the nature of the ~urfactant, when the~e alum~nosll~cat0~
are introduced into water ~ree ~rom ~ ctants. Th~refore, ~ t i~; advantageous that ~or the pur~f:~cation Or the precip~ta-ted crude products, aqueous solutions o~ the incorporated sur~actant are utilized ~or washing out the mother liquor.
"Ionic ~ actant~ res~stant to the acti~n of water h~rndes~ ~ormer~" within the meaning o~ the inventlon are anionic, cationic, or z~ritterionic water~oluble organ~c ~u~ace-act~ve compoun~ whlch e~n wh~n u~ed in ~11 con-centration~ and in the pre~ence of soluble salt~ caus~ng hardness, appreciably reduce the ~urfac~ tension ~nd which in their molecule contain an aliphatlc hydrocarbon re~i~ue ha~ng 8 tc) 26, pre:Eerabl~ 10 to 22, especlally 10 to 18, carbon atomsa or an alkylaromatic residue h~ving 6 to 18g pre~erably 8 to 16 aliphatic ~arbon atoms, a~d a~ ~i~nic and/or cationic group imparting solubility i~n water.
Zwitterionic sur:l~actants are ~ actants ha~ g molecules which contain anionic and cationlc group~ 5imUlta~ aOllSly.
me anionic ~urfactants comprise tho~e o~ the ~ulfonate, ~ ate, phosphonate ,, arld pho~phate types . In addition, compounds that are res~t~nt t~ the action of water hardness formers are also to be ~ow~d among the synthetic sur~ctEInts of the carboxylate type.
actants o~ the sul~ona~e type which are u~e~ul in the production o~ the product~ o:E the in~ention are alkyl-benzenesul~onates (C9_15 alkyls) or mixture~ o~ alkenesul-~onates and hydroxyalkanesul~onates, as ~11 a3 alk~nedisul-~onates, ~hich are prepar~d, for exampl~, by sul~onating monoolefin~ having terminal ~r non-terminal double bond~
u~ing gaseous sul~ur trioxide, ~ollowed by alkaline or 1~ 5~3U3~
acidic hydrolysiæ oi the sulfonation product~. Other ~uitable alXanesul~onate~ are the onesobtainable by the æulfochlorin-ation or ~ul~oxldation of alkane~, followed by hydrolys~3 or neutralization, or are obtainable by the additio~ of alkali metal bi~ul~ites to olefin~ Additional u~abl~ surfactants o~ the ~ul~on~t~ type are the ester~ o~ ulfo-~atty acid~, for example, the a-~ulfo acids derived ~rom hy~rogenated methyl or ethyl eæters of the ~atty acids derived from coconut oil, palm-kernel oil, or tallow.
Further suitable surfactants o~ the sul~onate type are the fatty acld ~steræ or amide~ of lower hydroxyalkane-sul~onic acids or amino-alkanesulfonic acids. Also u~able are the esters oi higher ~atty alcohols ~ith lo~er ~ul~o-carboxylic acids, ~uch as, for e~a~ple, sulfoacetlc acld, sulfos~cinic acid~ sulfobenzoic acid, sulfosalicyli~ acid, and ~ulfophthalic acid.
Suitable sur~actant~ of the sul~ate typ~ are the monoester~ of ~ulfuric acid ~ith primary higher fatty al~o-hols (~`or example, oleyl alcohol or primary alcohol~ deri~ed
2~ from coconut oil or tall~w~ or the monoeæters of ~ul*uric ac~d with secondary alkanols having ~ to 26 ~arbon atoms and mono- and die~ters o~ sul~urlc acid with terminal or internal higher alkanedlols. Like~i~e suitable are æulfated higher fatty acid monoglyceridesO Other 3uitable sur~actants of the sul~ate type which may be utilized are sul~ated non-ionics. In this ca~e the expresslon "non-ion~cs" de~ignates products obtained by the addition o~ 1 to 40, pre~erably 4 to 20~ molæ o~ ethylene oxide and/or propylene oxide to 1 mol o~ higher f~tty alcohol, higher alkylphenol, higher ~atty acid, hi~h~r ~atty a~ide, or higher alkylbenzene 105038~
sulfonamides or higher alk~ne3ulfonamide~. Especially lmpor-tant are the sulf~ted adducts of 2 to 8 mol~ of ethylene oxide with ~atty alcohols derlved from coconut oil or tallow, or with oleyl alcohol, or with secondary alcohols having fl to 18, preferably 12 to 14, carbon atoms, or with mono- or dialkylphenol~, having alkyl gro~aps containing 6 to 14 carbon atom~.
The sur~actants ~f the synthetic earboxylate type are also substances resistant to water hardnes~ ~ormer~
especially tho~e compound~, the molecule~ of which contain one or more earboxymethyl ether groups. ~xample~ of the sam~
are the carboxy~ethyl ethers of the abo~e-enumerated non-ionics, especially the ethoxylated hlgher ~atty alcohols (3 to 8 ethylene glycol ether groups per molecule). Addi-tional examples are carboxymethyl ethers of terminal or non-terminal higher alkanediols, higher fatty alcohol glycerol ethers or higher fatty alcohol pentaerythritol ethers.
All these anionlc surfactant~ are used as ~alt~
whereby the cations present c~n be the one previou~ly enumer-ated for the "Cat" in the alumino~ilicates.
Ju~t a3 in the a~ionic surfactants, the cationic sur~actants to be used according to the invention contain a stralght-cha~n or bra~ched-chaln aliphatic or cycloali-phatic hydrocarbon re3idue having B to 26, preferably 10 to 22, especially 12 to 18 earbon atom~ or an al~ylaro~atic or cycloalkylaromatic hydrocarbon res~ due ha~ing 6 to 18, preferably 8 to 16, aliphati c carbon atoms . The preferred basic groups are basic nitrogen atoms. Accordillglg, eligible 30 cationic sur~ace-active compounds can b~ allphatic, cyc~o-~OS~3~4 aliph~ic, alkyl or cycloalkylaromatic amine~ o~:p~imary, secondary, or tertiary character, gu~nidin or biguanidine derivati~es, compound~ containing heterocyclic nitrogen atom~, such a~, ~or example, deriva~ive~ o~ morpholine, p~r~dine, imidazoline, piperidine, etc~ Pre~erred are quaternary ammonium bas~s.
me hydrophobi~ residue and the group imparting water-solubility can be directly linked to each other or linked via hetero atoms or via hetero atom groups as, for example, by ether or thioether atom~, aminonitro~en atoms, carboxylic e~ter groups, carboxylic acid amide groups or ulYonic acid amide groups, etc.
In addit~on to the hydrophobic re~idue or residues, tha cationic ~u~factant~g especially the secondary, tertiary~
or quaternary ammonium bases, also contain group~ linked to the basic nitrogen, such a~ lo~er alkyl group~ having 1 to 4 carbon atoms, alkylol group~ having 2 to 4 carbon atom~ or aromatic hydrocarbon re~idue~, a~ ~or example~ ph~nyl or benzyl groups.
A~ e~amples ~or cationic ~urface-active compounds o~ tenside~ to be used according to the inYention, the follow-ing may be employed:
N-dodecyl-NI,~',N'-trim~thyl-1~3-diaminop~opane, octyl- or dodecyltrimethylammonium bisul~ate~
hexadecyl- or octadecyltrimethylammonium ~stho~ulfate~
bis (C12_18~alkyl)-dimethylammoni~m ehloride~
dibutylallyldodecylammonium chloride~ or ethylallylcyclohexyldodecyl ammonium chloride, ethylcrotyl- (diethylaminoethyl)-dodecylammonium ehloride, the orthophoephate of ~ ~uaternary base obtained by the ~ 3~S~
reaction of one mol o~ a ~atty amlne derived from tallo~ ~ith 10 mol~ of ethylene oxide, (C10_16-alkyl)-benzyldim~thylammonium chloride, (clo-l6-alky~ hlorobenzyl)-dimethylammonium bromide, dimethyl-dodecyl-(~-phenoxyethyl)-ammonium bromide, ~,C9_15-alkyltoluyl]-trimethylammonium chlorlde, benzyl-dimethyl-(p octylphenoxyethoxyethyl)-ammonium chlori~e, (C~ 6-alkyl)-dim~thyl-(naphthomethyl)-ammoDium chloride, dimethyl-(o-dimethylbenzyl)-dodecylammonium bromide, (Cg_ls-alkylphenyl)-trimethylammonium chloride;
in addition, organic ba~es or thcir ~alts in which the hydrophobic residues con~ain hetero atoms or hetero groups as~ ~or example:
(octadecoxycarbomethyl~-trim~thylammonium chloride, (dodecoxycarbomethyl)-pyridinium me~hosul~ate, (naphthenoxycarbomethyl)-~uinolinium chloride, (abiet~loxycarbomethyl~-~uinollnium bromide, di-(dodecoxycarbomethyl)-dime~hylammonium m~tho~ulfate, (octadecylaminocarbom~thyl)-trimethylammonium chloride, (octadecylanilinocarbomethyl)-pyridinium bi~ul~ate, (dodecoxymethyl)-trimethylammonium chloride, (octadec~lthiomethyl~-triethylammonium bisul~at~, (octadecylcarbamino~thyl)-pyridinlum chloride, (octadecyloxycarbaminomethyl)-pyridinium methosulfate.
The above organic nitrogen bases can be repl~ced with correspondingly constituted compound~ containing quaternar~ phosphoru~-~, ar~enic or other quaterna.~y atoms, or with compound~ containing a ternary ~ul~ur atom.
1 ~5~D3 ~ ~
It is to be understood that in thc pre~ent ca~e, cationic ~urfactants also include compound~ haYlng secondary or tertiary nitrogen atoms which contain alkylol groups linked to the nitrogen atom, as ~'or example, ethoxylation products o~ long-chain primary or ~econdary amin~s or reaction products o~ one mol o~ fatty acid or ~atty acid ester with at lea3t two mols o~ a dialk~lolamine, ~or example, diethanol-amine.
Each molecule oî the zwitterionic sur~ace-active 10 compoundæ to be u~ed according to the i.n~ention contains at le~st one of ths above-cited anio nic groups and one of the above-cited cationic groups. ~Iowe~rer3 several anionic and/or cat1onic group~ can be present. Pre~erably, equal nu~bera o~
anionic and cationic groups are present in one molecule.
The hydrophobic residue a~d the anionic or cationic group can be linked to each other dire~tly or Yia hetero atoms or hatero groups9 as ~or example, ~ia ether or thio-ether ~tomeg aminonitro~en atoms3 carboxylic acid e~ter group~, carboxylic aci~ amide groups, or sul~onic acid amide groups, etc.
In addition to the hydrophobic re~idue or residues contained in the cationic group~, other group~ ar e al~o l~ n~ed to the ba~ic n~,trogen, phosphorus, sulfur, or oxygen, such a~
lower alkyl group~ having 1 to 4 carbon atoms, alkylol group~
having ~ to 4 carbon atoms, or aromatic hydrocarbon resldlles, as f or examp~e, phenyl or benzyl group~ .
Suitable compounds o~ this ela~ are.~ ~or example, betaines, sulfateb~d3aine~, ~ul*obetaine~ and in ca~e~ in which a ~mall pho~phorus content i8 not di~turb~ ng, also 30 pho~phate-beta~nes. They can be represented b~ the follow-ing ~ormulae:
sulfonamides or higher alk~ne3ulfonamide~. Especially lmpor-tant are the sulf~ted adducts of 2 to 8 mol~ of ethylene oxide with ~atty alcohols derlved from coconut oil or tallow, or with oleyl alcohol, or with secondary alcohols having fl to 18, preferably 12 to 14, carbon atoms, or with mono- or dialkylphenol~, having alkyl gro~aps containing 6 to 14 carbon atom~.
The sur~actants ~f the synthetic earboxylate type are also substances resistant to water hardnes~ ~ormer~
especially tho~e compound~, the molecule~ of which contain one or more earboxymethyl ether groups. ~xample~ of the sam~
are the carboxy~ethyl ethers of the abo~e-enumerated non-ionics, especially the ethoxylated hlgher ~atty alcohols (3 to 8 ethylene glycol ether groups per molecule). Addi-tional examples are carboxymethyl ethers of terminal or non-terminal higher alkanediols, higher fatty alcohol glycerol ethers or higher fatty alcohol pentaerythritol ethers.
All these anionlc surfactant~ are used as ~alt~
whereby the cations present c~n be the one previou~ly enumer-ated for the "Cat" in the alumino~ilicates.
Ju~t a3 in the a~ionic surfactants, the cationic sur~actants to be used according to the invention contain a stralght-cha~n or bra~ched-chaln aliphatic or cycloali-phatic hydrocarbon re3idue having B to 26, preferably 10 to 22, especially 12 to 18 earbon atom~ or an al~ylaro~atic or cycloalkylaromatic hydrocarbon res~ due ha~ing 6 to 18, preferably 8 to 16, aliphati c carbon atoms . The preferred basic groups are basic nitrogen atoms. Accordillglg, eligible 30 cationic sur~ace-active compounds can b~ allphatic, cyc~o-~OS~3~4 aliph~ic, alkyl or cycloalkylaromatic amine~ o~:p~imary, secondary, or tertiary character, gu~nidin or biguanidine derivati~es, compound~ containing heterocyclic nitrogen atom~, such a~, ~or example, deriva~ive~ o~ morpholine, p~r~dine, imidazoline, piperidine, etc~ Pre~erred are quaternary ammonium bas~s.
me hydrophobi~ residue and the group imparting water-solubility can be directly linked to each other or linked via hetero atoms or via hetero atom groups as, for example, by ether or thioether atom~, aminonitro~en atoms, carboxylic e~ter groups, carboxylic acid amide groups or ulYonic acid amide groups, etc.
In addit~on to the hydrophobic re~idue or residues, tha cationic ~u~factant~g especially the secondary, tertiary~
or quaternary ammonium bases, also contain group~ linked to the basic nitrogen, such a~ lo~er alkyl group~ having 1 to 4 carbon atoms, alkylol group~ having 2 to 4 carbon atom~ or aromatic hydrocarbon re~idue~, a~ ~or example~ ph~nyl or benzyl groups.
A~ e~amples ~or cationic ~urface-active compounds o~ tenside~ to be used according to the inYention, the follow-ing may be employed:
N-dodecyl-NI,~',N'-trim~thyl-1~3-diaminop~opane, octyl- or dodecyltrimethylammonium bisul~ate~
hexadecyl- or octadecyltrimethylammonium ~stho~ulfate~
bis (C12_18~alkyl)-dimethylammoni~m ehloride~
dibutylallyldodecylammonium chloride~ or ethylallylcyclohexyldodecyl ammonium chloride, ethylcrotyl- (diethylaminoethyl)-dodecylammonium ehloride, the orthophoephate of ~ ~uaternary base obtained by the ~ 3~S~
reaction of one mol o~ a ~atty amlne derived from tallo~ ~ith 10 mol~ of ethylene oxide, (C10_16-alkyl)-benzyldim~thylammonium chloride, (clo-l6-alky~ hlorobenzyl)-dimethylammonium bromide, dimethyl-dodecyl-(~-phenoxyethyl)-ammonium bromide, ~,C9_15-alkyltoluyl]-trimethylammonium chlorlde, benzyl-dimethyl-(p octylphenoxyethoxyethyl)-ammonium chlori~e, (C~ 6-alkyl)-dim~thyl-(naphthomethyl)-ammoDium chloride, dimethyl-(o-dimethylbenzyl)-dodecylammonium bromide, (Cg_ls-alkylphenyl)-trimethylammonium chloride;
in addition, organic ba~es or thcir ~alts in which the hydrophobic residues con~ain hetero atoms or hetero groups as~ ~or example:
(octadecoxycarbomethyl~-trim~thylammonium chloride, (dodecoxycarbomethyl)-pyridinium me~hosul~ate, (naphthenoxycarbomethyl)-~uinolinium chloride, (abiet~loxycarbomethyl~-~uinollnium bromide, di-(dodecoxycarbomethyl)-dime~hylammonium m~tho~ulfate, (octadecylaminocarbom~thyl)-trimethylammonium chloride, (octadecylanilinocarbomethyl)-pyridinium bi~ul~ate, (dodecoxymethyl)-trimethylammonium chloride, (octadec~lthiomethyl~-triethylammonium bisul~at~, (octadecylcarbamino~thyl)-pyridinlum chloride, (octadecyloxycarbaminomethyl)-pyridinium methosulfate.
The above organic nitrogen bases can be repl~ced with correspondingly constituted compound~ containing quaternar~ phosphoru~-~, ar~enic or other quaterna.~y atoms, or with compound~ containing a ternary ~ul~ur atom.
1 ~5~D3 ~ ~
It is to be understood that in thc pre~ent ca~e, cationic ~urfactants also include compound~ haYlng secondary or tertiary nitrogen atoms which contain alkylol groups linked to the nitrogen atom, as ~'or example, ethoxylation products o~ long-chain primary or ~econdary amin~s or reaction products o~ one mol o~ fatty acid or ~atty acid ester with at lea3t two mols o~ a dialk~lolamine, ~or example, diethanol-amine.
Each molecule oî the zwitterionic sur~ace-active 10 compoundæ to be u~ed according to the i.n~ention contains at le~st one of ths above-cited anio nic groups and one of the above-cited cationic groups. ~Iowe~rer3 several anionic and/or cat1onic group~ can be present. Pre~erably, equal nu~bera o~
anionic and cationic groups are present in one molecule.
The hydrophobic residue a~d the anionic or cationic group can be linked to each other dire~tly or Yia hetero atoms or hatero groups9 as ~or example, ~ia ether or thio-ether ~tomeg aminonitro~en atoms3 carboxylic acid e~ter group~, carboxylic aci~ amide groups, or sul~onic acid amide groups, etc.
In addition to the hydrophobic re~idue or residues contained in the cationic group~, other group~ ar e al~o l~ n~ed to the ba~ic n~,trogen, phosphorus, sulfur, or oxygen, such a~
lower alkyl group~ having 1 to 4 carbon atoms, alkylol group~
having ~ to 4 carbon atoms, or aromatic hydrocarbon resldlles, as f or examp~e, phenyl or benzyl group~ .
Suitable compounds o~ this ela~ are.~ ~or example, betaines, sulfateb~d3aine~, ~ul*obetaine~ and in ca~e~ in which a ~mall pho~phorus content i8 not di~turb~ ng, also 30 pho~phate-beta~nes. They can be represented b~ the follow-ing ~ormulae:
3~4 I3 Rl - N - R~ - X
~ Y 13 II) R3 - ~ N _ R5- N ~4 ~ X
- Rl - Rl ,, l3 III) R6 ~ ~ i ~ R5 - ~ X
Z ~2 .
In these formulae~
~1 is an aliphatic, cycloal~phatic, or alkyla~omatic group having 10 to 22 carbon atoms, prefe~ably a straight-chain alkyl group having 12 to 22 carbon atoms, R2 is an alkyl group having 1 to 4 c~rbon at~ms, or an alkylol group having 2 to 4 carbon atoms, or a polyether residue havin~ the formula - ( CH2-CH2-0) m~H
in which m = 2 to 5, R3 i~ the group R2 or a phenyl, ben~yl or toluyl group, R~ is an alkylene group or a hydroxyalkylene group - having 2 to 4 carbon atom~, R5 is an alkylene group ha~ 2 to 4 carbon atoms~
R6 is a saturated or ethylenically-unsaturated, pre~
~erably stralght-ch~in hydrocarbon ~esidue ha~lng , .
. 9 to 21, especially 11 to 17 carbon atoms~
~6~3~
X are the groups -C00~, -0-S03-, or -S03-, Y are the groups H or X, Z are the grollps H or R2, and n is an integ~r ~rom 1 tlD 100.
Betaine~ ha~ing the fo:rmula I are prepared by cau~ing tertiary amine of the ~o:rmllla RlR2R3N to react with halocarboxylic a6ids, for ~xample, chloroacetic acid, bromo-acetic acid, or a-chloropropionle acid, or b~ quaternizing in suitable Dlanner aninocarboxylic acids or the product of the react~:on o~ secondary amine~ with acrylic acld. Sul~ate betaines are analogou~ly obtainable by the react3~on oi the tertlary ~m~ne 8 with the e ~ters or ~alt~ ~ haloalkylsul~uric acids. Sul:eobetaines are obtainable by the reaction of the tertiary amine~ ~ith haloalkylsulf`onic acids or sulto~es3 e~pec~ally wlth propane~ultone.
Formula II includes example. ~or compound~ having ~everal betaineg sul~ate-betaine, or ~ul:eobet~lne grou~
To prepare these compounds, polyethyleneimin2, polypropylen~
imine, or polybutylenimine are alkyla ed, and then reacted in the above-mentioned manner with halocarboxylic acid~, haloalkyl~uliuric ac~d esters, haloal~ylsul:fonic acid~ or sultones. Alternativ~ly, the polyethylenelmineæ can be ~ir~t ca~sed to react with acrylic acid derivatives and then be alkylat~d by introduction o~ the gro~p Pcl. Compounds o~ the i~ormula III can be obtaincd when natural or synthetic ~atty acid~ are condensed ~ith ethylenediamine, N-alkyl-ethylenediamine or N-hydroxyalkylethylened:iamine, ~ollowed by reaction ~rith halocarboxyli~ acids, haloalkylsul~uric acid ester~ or haloalkyl~ul:eonic acids or sultone~. In addl-tion to the above methods o:P preparation, other methods 3~g~
can be u~ed, ~or example, the reactlon of te~tiary amines ~ith epichlorohydrin, ~ollowed by the introduction of sul~ate or sul~onate groups.
~ xamples of these zwittlerionic sur~ace-active com-pounds are:
N-alkyl-N-dim~thyl-am~onium-methyl carboxylate, N-alkyl-N-benzyl-N-methylammonium-methyl carboxylate, N-alkyl~N-bis-(2-hydroxyethyl)-ammonium-methyl carboxylate, N-alkyl-N-diethylammonium-ethyl carboxylate~
2-alkyl-1-(~-hydroxyethyl)-imidazollnium-1-methyl carboxylate, 3-(N-alkyl-N-dim~thylammonium)-2-hydroxypropyl-sul~ate, 3-(N-alkyl-N-dimethylammonium)-propane-sulfon~te, and 1-(3-trim~th~lammonium)-alkane-sulfonate, in which the alkyl or the alkane group~ preferably are long-chain hydrocarbon re~id~es having 10 to 22~ pre~erably 12 to 18, carbon atoms and can be, ~or example, derived ~rom natural ~atty re~idues, such a~ are obtainable from coconut oil or tallow.
In the ne~ compounds, the urfactants c~n be Bound to the sur~ace of the aluminosilicate particles, but they can be also embedded in the alumina~llcates. In mo~t case~, they are adsorbed on the surface as w~ll a~ embedded in the aluminosilicate~
Surfactant~ havlng bulky hydrophobic res~due~ (for example, sueh a~ ~rith branched chain~ or ring ~ystem~) have been æhown to be more solidly anehored in the new compound~
than those having straight-chain aliphatic residue~. The latter ~ur~actant~ are easier dissolved out ~rom the alumino_ silicate than the f ormer when the new compounds vr their 30 suspensions are introduced into water.
_ 14 -~ ~5~D3 8 ~
Of special in~erest are the new compound~ which have been prepared ~rom cationic or zwitterionic surf`actants whlch likewi~e can be ~ound to the surface o~ the alumino-~ilicates. They can be also embedded in the aluminosilicate~.
In most cases, e~pecially the catLonic surfactants ~re not on~y adsorbed on ~he sur~acs (i.e., they ~orm a part of the previously mentioned cation "Cat" when the compo~ition of the aluminosil~cate~ was di~cuæsed), but they are al~o embe~ded ln ths alumino~llicates.
In aqueou~ solution, the new sur~actant-containing alumlnosilicate ~ub~tances relea~e the bound ~urf~ctants.
m erefore, the types charged ~ith anionic or zwit~erionlc ~ur~actants are suitable as additives to washing and cleaning liquors. The alumlnosilicates charged ~ith cationic surfac-tants are distinguished by a remarkable adsorption power for d~ssolved dye~tu~s or d~spersed pigments, hence can be used as adsorpti~e agents ~or such substanc~s. In case the catlonic sur~actants ha~e antimicrobial properties, the new compounds can be used wherever a gradual release of the cationic ~ur 20 ~actants to the ~urrounding liquid is de~ired.
The ~ollo~ing example~ are illustrative of the pr~Lctice of the invent~on ~ thout being limitati~ o~ the ~ame in any respect.
E X A M P L E S
The ~urI actant-containing alumino~ilicates o~ the in~entit)n are manuL~actured accordi ng to the following dlrec-tions unleæs ~nother m~thod of operation i~ expre~ly stated.
A solution o~ the surfa~a-active compound ( sur~ac-tant) and an alkali metal silicate in deioni~ed water was l~SO3l~4 introduced into a one-liter vessel and while mixing wi-th a high-speed intensive stirrer (10,000 rpm, "Ultraturrax", made by Janke ~ Kunkel IKA-Werk, Stauffen/Breisgau, Germany), the aluminate solut~n was then added in small portions.
Immediately before use, the solu-tion of Na20 . 8 SiO2 had been prepared from finely divided, easily alkaline-soluble silicic acid and commercial water glass. After stirring had been continued for 30 minutes, an alîquo-t part of the alumino-silicate suspension which had been formed was separated for isolating the aluminosilicate. For this purpose, the solution was filtered with suction from the solid which had been formed, and the residue on the filter was washed with deionized water.
The residue on -the filter was dried a-t 80C for -three hours under 100 mm Hg pressure and then analyzed. The yields of the products thus dried amounted to 70% to 95% of the theore-tical.
The water content was determined with Fischer's reagent and for the determination of the amount of the anionic or cationic surfactants, 0.5 gm of the new product were dissolved in 50 ml of lN H2S04 at boiling, followed by titration of the surfactant according to Reid et al, "Tenside", Vol. 4 (1967), pp. 292-304. For the determination of the zwitterionic surfactants, the DGF Standard Method H III 4 (65) was employed. (DGF-Einheitsmethoden, S-tuttgart, 1969 --DGF ~ Deutsche Gesellschaf-t fur Fettwissenschaften, German Society for the Science of Fats.) All data given in % are percent by weight. The contents of surfactants are based on the precipitation pro-duct which has been dried in the above-described manner and still contains bound water. If these contents were to be ~0~)384 computed on the basis o~ the m$xture o~sur~actant and anhy-drous inorganic active su~stance, somewhat h~.gher values would be obtainPd.
Comparative substances were p~ pared under the same conditi~ns, e~cept that sur~aetants were omitted from the startlng solutions. These compo~lds and the compounds ~ the invention were compared in the determination of the Ca~eques-tering power according to the fol:Lo~ing method:
One gram o~ the product dried in the above_de3cribed manner (on an AS basis) was stirred a~ 50C for 15 minutes with one liter of a solution of 0.7~65 gm o~ CaC12 2 H20/
liter (equal to 30 dH - German hardneæs) which had bee:n ad,~usted to a pH o~ 10. A~ter the ælum~n7lm silicate ha~ been filtered of~, the resldual hardness "x" of the ~il1;rate was determine~ from which the Ca-sequesterlng power ~as computed in mg CaO/gm AS according to the iormula: (30-~) . 10.
The sur~actants which were used, the anlonic sur-~ace-active compounds or anionic sur~actants being present a~
Na-salts, were designated b~ the following abbreviat~ons:
2C "ABS" desi~nate~ the salt of an alky~benzene-sul~onic ac~d having 10 to 15, pre~erably 11 to 13~
carbon atoms in the alkyl ~hain, ~ich acid had been prepared by the cond~n~atlon of straight-chaln olefins with ~enzene, followed by sulionation o~ the al~
benzene thus formed~
"TPS" designate~ the salt of an alk;ylbenzene-sul:Eonic acid having 9 to 15, pre~erably 12, carbon atoms in ~e alkyl chainl whlch acid had been prepared by the cond2nsation o~ technical tetraprop~lene with benzene, ~ollowed by sul~onation of the alkylbenzene thus ~ormed.
~0 ~ 3 ~ ~
"MS" des~gnate~ the salt of a mixture of alkanemono-~ulfonates and alkanedisulfonates ~"Mersolat"), which mixture has been prepared by sulfochlorination o~ a C12_~8-par~rfin~ saponi~icat,ion o~ the sulfochloride thus formed with aqueous sodium hydroxide and separation o~ the non-converted paraffin mixture from the sulfonate~
"FAS" designates the sulfate of dodecyl alcohol.
"FA-E0-S" designates the sulfate of an adduct of two mols of ethylene oxide with one mol o~ a fatty alcohol derived from coconut oil.
"OS" designates a sulfonate th~t has been preparea ~rom a-ole~in mixtures having 15 to 18 carbon atoms by sul~onation with S03 and hydrolysis o~ the sulfonation product with aqueous sodium hydroxîàe, whlch sulfonate essentially consists of alkenesul~ona~e and hydroxy-alkanesulfonate and which, in addition, contains small quantitie s of` alkanedi sulf on~te s .
"FA-E0-C~" designates the carboxymethyl ether of an adduct of 4.5 mols of ethylene oxide with one mol of a ~atty alcohol derived ~rom coconut oil.
"CTMA" - ce~yltrimethylammonium chloride . "CTMB" = cetyltrimethylammonium bromide "~TMA" = lauryltrimethylammonium chloride "~YPC" = laurylpyridinium chloride "L~DM" - laurylbenzyldi~.~ethylammonium chloride '9~DBD" = lauryl(d~chlorobenzyl)dimethylammonium chloride "TDM~" = dl-(palmityl/stearyl)-di~ethylammoniu~
chloride, where the palmityl/ste~ryl alkyl mixture is d~ri.ved ~rom tallow ratty acids.
1~ ~ 3 EXAMPLE Al __ Precipitation: 0.5 gm o~ ABS in the ~orm o~ a 20%
technical solution and 90.4 gm o~ a 25~ aqueous ~olution of Na20 ~ 8 SiO2 dissolved in 300 ml o~ deionized water were precipltated wlth a ~olut~on o~
27.L~ gm of sodium aluminate (41~ Na20, 54~ A1203) in 80 ml o~ water.
Composition of the 1.3 Na20 A1203 2-9 SiO2 5-1 H20,dried precipltatioh product: 009% A~S.
Concentration of the su~pension: 9.1% solids having the above compo~ition.
Ca-seq~estering po~r: 110 mg CaO/gm AS.
~XAMPIæ A2 Precipitation: As in ~xample Al, except thRt 1.0 gm oi AB~ wa~oused.
Compositlon o~ the 1.2 Na20 A1203 2~8 SiO2 ~ 6.4 H20, dried precipitation product: 1.5% ABS.
Concentration o~
the ~uspension: 9.5~ soli as ha~ing the above composition.
Ca-sequestering power: 109 m~ CaO/gm AS.
Precipitation: As in ~xample Al, except that 2.5 gm of ABS were u~ed.
Composition of the 1.2 Na20 A1203 2.9 S102 ~.B H20, dried precipitation product: 3.5% ABS.
Concentration of the suspension: 9.3% solias having the above composit~on, Ca-sequestering power: 114 mg CaO/~m AS.
- 19 ~
~L6gS~3~9~
Precip~tation: As in Example Al~ except that 5 gm of ABS were u~ed.
Composition of the 1.2 Na20 ~ A1203 2.9 SiO2 4-2 H20, dried precipitation product: 6~3% ABS
Concentration o~
the suspension: 9.4% 301id~ havlng the abo~e composltion.
Ca-s~questering power: 107 mg CaO/gm AS.
EXAMPLEA~
Precipitation: As in ~xampls Alg except that 10 gm of ABS ~ere u~ed.
Composition of the 1.2 Na20 A1203 3.2 SiO2 6.3 H20, dried precipitation product: 1105~ ABS.
Concentration of the suspension: 10.2~ solids ha~ing the above composition.
Ca-sequestering power: 110 mg CaO/gm AS.
Precipitation: As in ~xample Al, except that 50 gm o~
ABS were used.
Composition of the 1.3 Na20 Al2o3 2-7siO2 ~ 3 9 ~2 dried precipitation product: 33.4% ABS.
Concentration of the suspension: 11.7~ solids having the abo~e composition.
Ca-sequestering power: 105 mg CaO/gm AS.
_ 20 -5~31~
~XAMPLE A7 Precipitation: A~ in ~xample Al, except that 1 gm of TPS wa~ used in the ~orm of a ~olution containing 20 gm/liter.
Composition of the 1.2 Na~O A1203 2-a S102 ~-4 H20, dried precipitation product: 1.7~ TPS.
Concentration of the su~pension: 9.5~ solids having the above composition.
Ca-sequestering - power: 108 mg CaO/gm A~.
, Precipltation: As in Ex~mple Al, exc~pt that 1 gm of MS
was used in the form o~ a solution con-taining 20 gm~liter.
Composition of the 1.1 Na20 A1203 2.7 SiO~ 4.1 H20 , dried precipitation product: 0.1% MS.
Concentration of the suspension: 8.9% solids ha~ing the abo~e composition.
Ca-sequestering power: 104 mg GaO/gm AS.
EXAMPL~ A9 Precipitation: As in ~xample Al, except that 1 gm of FAS was used in the form of a ~olution containing 20 ~m/liter~
Composition of the 1.2 Na20 A1203 ~ ~.9SiO2 6.4H~o, dried precipitation product: 0.1% FAS.
Concentration of the suspension: 9.3~ solids having the abo~e composition, Ca-sequesterlng po~er: 111 mg CaO/gm AS.
:1~5~3~34 ~XAMPLE A10 __ Precipitation: As in Example Al, except th~t 1 gm of Fa-~O-S wa~ ueed in the iorm o~ a solutiom containing 20 gm/liter, Composition of the 1.2 Na20 A1203 . 2-9 SiO2 6-1 H20, dried precipitation product: 0.1% Fa-~O-S.
Concentration of the suspension: 9.3~ solids having the abov~ composition.
Ca-æequestering power: 120 mg Cao/gm AS.
EXAMPLE All Precipitation: As in ~xample Al~ ~xcapt that 1 gm o~ OS
was u~ed in the form of a solution con-taining 10 gm/liter~
Composition o~ the 1.2 Na20 A1203 2.8 SiO2 6~7 H20, dried precipitation product~ 0.1% OS.
Concentration of the suspension: 9.~% solids having the above composition.
Ca-sequestering power: . 108 mg CaO/gm AS.
Precipitation: As in Exa~ple Al, ~xcept that 1 gm o~
Fa-~O-CME wa~ uæed.
Composition o~ the 1,2 Na20 A1~03 2.9 SiO2 5-3 H20, dried precipitation product: 0.2~ Fa-EO-CME.
Concentration of the suspension: 9.1% solids ha~in~ the above composition.
ca-sequestPring power: 98 mg CaO/gm AS.
~5~33~4 _omparison Test_with Re~erence to Examples Al to A12 ~recipitation: As in Example Al, except that no sur-factant was used.
Composition of the 1.2 Na20 A1203 2.8 SiO~ 5.3 H?0, dried precipitation product: 0.00~ surfactant.
Co~centration of the suspension: 9.1~ solids having the above compositio~.
Ca-sequestering power: 90 mg Cao/gm AS.
When the products according to Examples Al to A12 were compared with the product of the comparative test, with reference to the stability o~ the a~ueous suspensions, this comparison shows that the sedimentation rate in the product of the comparative test is considerably higher, which means that the products according to the ~nvention can be held for a longer period of time without depositing sediment. Further-more, the products according to the lnvention show a higher cation exchange capacity than the products without the addition of surfactants.
~.
~L~5038~
Precipitation: 0.1 ~m o~ ABS in the form of a technical 20% solution and 9.05 gm o~ a 25% aque-ous solution of Na20 8 SiO2 d~ssolved in 400 ml of deionized water were reacted ~lth a solution of 5.50 gm o~ sodium aluminate (41~ Na20; 54~ A123) in 80 ml of water.
Composition of the 1-2 Na2 A1203 0 2-7 SiO~ 6.4 ~2-dried precipitation product: 0.7% ABS.
Concentration o~
the ~uspension: About 2~ æolids ha~ing the abo~e compo3ition..
Ca-sequestering power: 105 mg Cao/gm AS.
Precipitation: 4 gm o~ ABS in the form of a 20~ tsch-nical solution were dissolved in 10 ml of deionized water and mixed with 361.6 gm of a 25% solution o~ Na20 -8 SiO2. To th~s solution~ 10906 gm o~
solid sodium aluminate (41% Na~0, 54~
A1203) were added in proportions while stirring vigorously.
Composition of the 1.2 ~a20 A1203 2.7 SiO2 5.1 ~2 dried precîpitation product: 2~ ABS.
Concentration of the suspension: 37.2% solids having the above composition.
Ca-sequestering power: 98 mg Cao/gm AS.
- 24 - ~
~L~5~384~
.
Precipitation: 1~0 gm o~ ABS in the ~orm of a 20%
technical solution and 32.6 gm of soaium aluminate (41% Na20; 54% A123) were di~solYed in 300 ml of deionized water.
The solut1on was treated wlth 70 gm of a 25% Na20 8 SiO2 solution ln 100 ml o~ wat~rO
Composition of the 1~1 Na20 A1203 1.6 SiO~ 4.8 H209 dried precipitation product: 1.6~ ABS.
Concentration of - the suspension: 9. 2% solids ha~ing the abo~e composition.
Ca-s~questering power: 115 mg CaO/gm AS.
Precipitatinn: 1.0 gm o~ ABS in the form of a 20%
technical solution and 18.8 gm o~
sodium alumlnate (41~ Na20; 54~ A1~03) were dissolved in 300 ml of deionized water, This solution was treated with a ~olutlon o~ 124.5 ~m of a 25% solu-tion o~ Na20 8 SiO2 in 100 ml of . -water.
Composition of the 1.5 Na20 A1203 3-~si02 5-2 H20 3 dried precipitation product: 1.7~ ABS.
Concentration of the suspension: 9.9~ solids ha~ing the abo~e composition.
Ca-sequestering power: 116 mg CaO/gm AS.
- 25 -.
~95~313~
Precipitation: 0.1 gm o~ AB~ in the form of a 50%
technical paste and 148 gm o~ a 35%
aqueous solution of Na20 3 . 46 SiO2 dis~ol~red ii~ 637 gm deionized water w~re treated w~th a solution of 54~8 gm o~ sodium aluminate (41~6 Na20; 54%
- A1203 ) in 160 gm of water .
Composition of the 1.25 Na20 A1203 2-75si02 4 H2 dried precipitation product: . 0.032~ ABS.
Concentration of the suspension:. About 10% solids ha~ing the above composition.
Ca-sequestering - ~ower: 100 mg CaO/gm As.
In order that the low content of surfactant in the precipitation product according to Example A17 could be determined with sufficient accuracy, the amount o~ substance ~b~ained in three batches was extracted with alcohol, and the solution thus obtained was concentrated and titrated as described above.
?
~S~;!1384 EXAMPLE Kl Precipitation: 0.5 gm o~ CTMA i~ the Porm of a 25 technical solutlon and 90.4 gm of a 25~ Na20 8 S~02 solution were d~ssolved in 300 ml deionized water. This solution was treated with a solutinn o~ 27.4 gm of sodium aluminatc (41% Na20; 5~%
A1203) in 80 ml of water.
~Composition of the 1.2 Na20 A1203 2o9$i02 6-4H
dried precipitation product: 0.9% CTM~
~oncentration of the suspenslon: 9.4% solidæ having the aboYe composition.
ca-sequestering power: 109 mg CaO/gm A5.
EXAMPL$ K2 Prècipitation: As ln Example Kl, except that 1.0 gm of CTMA was used.
Composition o~ the 1-2 Na2 A1203 2-8 SiO2 6.8 H20, dried precipitation product: l.9~o CTMA.
Concentration of the suspension: 9,~ sollds having the abo~e composit~on.
Ca-sequestering power: 113 mg CaO/gm AS.
~XAMPLE K3 -Precipitation: As in Example Kl, except that 2.5 gm of CTMA ~ere used.
Composition of the 1.1 ~a~o A1203 ~ 3.1 sio2 ~ 5.5 ~2~
dried precipitation product: 4.6% CTMA.
Concentration of the ~uspen~ion: 9. 5% solidæ haYing the above composition.
Ca-sequestering power: 121 mg Cao/gm AS.
~XAMPLE K4 Precipitatlon: As in Exam~le Kl, except that 5 gm Or CTMA w~re u~ed.
Composition of' the 1.3 Na20 A1203 3.2sio2 ~ 5.4 H~O, dried precipitation product: 603% CTMA.
Concentration of the suspension: 9.9~ ~olids having the above composition.
Ca-sequestering power: 114 mg Cao/gm AS~
E MPLE E~
P:recipitation: As in Example Kl, except that 1() gm Or CTMA were used.
.Zomposition oi the 1,2 Na20 A1203 ~ 2.9 SiO2 ~ 4-~ ~2~
dried precipitation product: 15.3~ GT~A.
Concentration of' the suspenslon: 10.8% solids having the abova composltion.
Ca-sequestering power: 128 mg CaO/gm AS.
~1[)5038~
__ Precipitation: A~ in ~xample Kl, except that 50 gm of CTMA ~ere u~ed.
Composition o~ the 1.2 Na20 A1203 2-8 SiO2 5-7 H20 dried precipitation product: 14.3% CTMA.
Concentration of the su~pension: 10~4% solids haYing the above composition.
Ca-sequestering power: 122 mg Cao/gm AS~
.
Precipitation: As in ~xample El9 except that 1 gm of LTMA was u~ed.
Compo~ition o~ the 1.3 Na20 A1203 2-9 SiO2 5-3 H20, dried precipitation product: .1.4~ LTMA.
Concentration o~
the suspension: 9.2% ~olids having the above composition.
Ca-sequestering po~er: 115 mg CaO/gm AS.
~XAMPLEK8 Precipitation: As in Example Kl, except that 1 gm of BPYC wa~ used.
Composition o~ the 1.1 Na20 A1203 2.8 SiO2 ~ 6.5 H20 , dried precipitation product: 1.2~ ~P~C.
Concentration of the suspension: 9.5% solids having the above compositionO
Ca-sequestering power: 107 mg Cao/gm AS.
1051~384 Comparison Test with reference to ~xam~les Kl to K8 Prec~pitation: A~ ln Exampl~ Kl, except that no suriactant Wl16 added.
Composition o~ the 1.2 Na20 A1203 2-8 ~i2 5-3 H20 dsied preclpitation pr~duct: 0.00% ~urfactant Concentration of the ~uspension: 9.1% solids ha~ing the abo~e composition.
. ~a-sequestering 10 po~er: go mg CaO/gm AS.
When the suspensions prepared according to Example~
Kl to K8 were compared with the suspension of the comparative -- test~ this compari~on shows that the latter ~uspension ha a considerably higher s~dimentation rate, which means that - ~ the suspen~ion~ according to the in~ention can be stored -~or a longer period o~ time without deposit~ng sediment.
Precipitation: 0.1 gm o~ CTMA in the ~orm of a 25 . technical solution and 9.05 gm of a 25~
NaO2 8 SiO2 solution were dissolved in 400 ml deionized water. This solution ~as treated with a solution of 5.50 gm of sodium aluminate (41~ NaO2; 54 A1203) in 80 ml of water.
Composition o~ the -1.1 Na20 A1203 2.7 SiO2 5.6 H20 , dried precipitation product: about 2% of CTMA
Concentration of the suspension: 1.8~ solids having the above composition.
Ca-sequestering power: 116 mg CaO/gm AS.
_ 30 -~0503~34 EXAMPL$ K10 .
Precl.pitation: 4 gm of CTMA in the form of a 25% tech-nical solution were dissolved in 10 ml of deionized water and mixed with 361.6 gm o~ a 25% Na20 ~ 8 SiO2 solution.
109.6 gm o~ ~olid ~odium aluminate ~41~ Na20; 54% A1203) were added in:por-tions to this solution while stirring - Yigorously.
Co~position o~ the 1.3 Na20 ~ A1203 . 3-3 SiO2 7-4 H~O, dried precipitat~on product: 1.9% CTMA
~oncentration o~
the suspension: 38.3% solids ha~tng the above compos~tion.
Ca-sequestering p~w~r: 9~ mg CaO/gm AS.
~XAMPLE Kll Precipitation: 1.0 gm of ~TMA in the ~orm of a 25 technical solution and 32.6 gm of sodium aluminate (41~ Na20; 54~ A1203) were dissolved in 300 ml deionized water. This solution was treated with a solution of 70 gm o~ a 25% Na~O 8 SiO2 solutlon in 100 ml of water.
Composition o~ the 1.0 Na20 A1203 1-6 SiO2 5-3 H20, dried precipitation product: 1.5~ CTMA.
Concentration o~
the suspension: 9.2% solids ha~lng the abo~e composition.
Ca-sequestering power: 115 mg CaO/gm AS.
- 31 ~
~XAMP~E K 12 .
Precipitation: 1.0 gm of CTMA *n the form o~ a 25~
technical solution and 18.8 gm of sod~um aluminate (41% Na20, 54~ A1203) were dissolved in 300 ml o~ de~onized water.
This solution wa~ treated with a solution of 124.5 gm of 25~ Na20 8 SiO2 solution in 100 ml o~ water.
Composition o~ the 1.5 Na20 A1203 3.8 SiO~ ~ 5.2 H~O , dried precipitation product: 1.9% CTMA, Concentration o~
the suspension: 9.7~ solid~ ha~ing the above compo~ition.
Ca-sequestering power: 108 mg CaO/gm AS.
E ~
Pre~ipitation: As in Example Kl,.except that 1.0 gm of . LDBD was used.
Composition of the 1-2 Na20 ~ A1203 2-8 SiO2 5-4 H20 dried precipitation product: 1.8% LDBD
Concentration of the suspension: 9.7% ~olids ha~ing the abov~ composition.
Ca-sequestering power: 110 mg Cao/gm AS.
.
Precipitation: As in Example Kl, except that 1.0 gm of 1BDM was used .
Composition of the 1.2 Na20 A1203 2.7 S102 ~ 5.9 H20, dried precipitation product: 1. 7~ ~BDM~
Concentration o~
the suspension: 9.5% ~olids having the abo~e composition.
Ca-sequestering power: 116 mg Cao/gm AS.
~5~384 BXAMPLE Kl~
Precipitation: A~ in ~xample Kl, except that 1.0 gm of TDMA ~as used.
Composition of the 1.2 Na20 A1203 2-8 SiO2 5-7 H20, dried precipitation product~ % TDMA.
Concentration of the suspension: 9.7% solids ha~ng th~ above composition.
Ca-sequestering power: 114 mg Cao/gm AS.
~XAMPLE K16 Precipitation: As in ~xample Kl, except that 1.0 gm of CTMB was used.
Composition o~ the 1.1 Na20 A1203 2.9 SiO2 ~ 4.8 H20, dried precipitation product: 1.9~ CTMB.
Concentration of the suspension: 9~9~ solidæ having the above composition.
Ca-sequestering power: . 108 mg Cao/~m AS.
Precipitation: A~ in ~ample Kl, except that 5 gm of N,N-didodecylamine w~e used in place of the CTMA.
Composition of the 1-37Na20 A1203 2.7 SiO2 ~4018 H20 +
dried precipitation product: 705% N,N-didodecylamine.
Concentrati~n of the suspension: About 10% solids having the abo~e compositlon.
Ca-sequestering power: 115 mg CaO/gm AS.
- 3~ -~05~1138~
~XAMPIE K 18 Precipitatlon: A~ in Example Kl, except that 5 mg of ~-dodecyl-N,N-dimethylamine were u~ed in place of the CTMA.
Sompo~ition of the 1.32 Na20 A:1203 2.57 SiO2 ~ 4.52H20 dried precipitation product: 1.6~ o~ N-dodecyl-N,~-dimethylamine, Concentration o~
~he suspension: About 10% solld~ ha~ng the abo~e compo~ition.
Ca-se~uestering power: 115 mg CaO/gm AS.
EXAMPLE Kl9 __ Precipitation: A~ in Example gl~ except that 5 gm of octylamine were used in place of the CTMA.
Composition of the 1.01 Na20 A1~03 :2~,3-9SiO2 3.87 ~2 +
dried precipitation product: 3.1~ octylamine.
Concentration o~
the suspension: About 10% solids ha~ing the abo~e composltion.
Ca-sequestering power: 110 mg Cao/gm AS.
EXAMP~E K20 Precipitation: As in Example Kl, except that 5 gm o~ a tertiar~ a~lne group containing C12_18 coconut oil fatty acids-polydiethanol_ amide (obbRined as the condensation pro-duct of 1 mol of coconut oil ~atty acid~
and 2 mols of diethanolamine3.were used.
Composition of the 1.36 Na20 A1203 2-38S~02 3~78H20 +
dried pr~cipitation 3 4~ coconut fatty acid-polydiethanOlam Concentration of the suspension: About 10% solids ha~ing the aboYe composition.
Ca-sequestering ~ power: 120 mg CaO/gm As.
- 3~ -~AMPLE K21 iO ~ 3 84 Precipitation: 50 mæ of CTMA i~ the form of a 25~
technical solutlon and 148 gm of a 35%
aqueous solution o~ Na20 3.46 SiO2 were dissol~ed in 637 gm o~ deionized water. This solution was tre~ted with : ~ solution of' 54.8 g~ of sodium alum-~nate (41~ Na2, 54~ A1203) in 160 gm . . of water.
Composition of the 1.25Na20 A1203 ~ 2.75 SiOz 4 H20, dried precipL~a~ion pro~uct: 0.02~ CT~
Concentration of the suspension: About 10~ solids ha~ing the above co~position.
Ca-sequestering power: 100 ~g CaO/gm A5.
.:
In order that the lo~ content o~ sur~ctant in the precipitation product o~ Example K 21 could be datermined with sufficient accuracy, the quantity o~ substanc~ obtaine~
in three batches ~ras extracted ~ith alcohol, and the solutinn th~s obt~ined was.concent~ated and tested as described above.
EXA~P~E Zl Precipitation: - As in Example Al, ~xcept that 1 gm o~
a beta~ne having the formula -C12H~5 j N \ - C~2 - COO
C~3 C~3 was ~dded-to the sodium silicate solutlon . ) in place of the ABS.
Co~position o~ the 1.3 Na20 A1203 2.7 SiO2 5.6 H20 dried precipit2~ion 30 product: 0.05~ betaine. .
Concentration o~
the suspension: 9.4% solids havin8 the above compositicn.
Ca-sequesterin~ .
power: 103mg CaO~gm AS.
, . ~ 35 .
~05~)3~3~
.
Precipitat~on: As ln Example Z1, except that 5 gm of the betaine were used.
eomposition of the 1.2 Na20 ~ A1203 . 208 SiO2 409 H20 dried prec~pitation product: o.o6~ betaine.
Concentration of the suspension e 90 5% sol~d~ having the abo~e composltion.
Ca-sequestering p~wer: 105 n4~ CaO/gm AS.
Precipitation: As in Exampl~ Zl, except that 25.0 gm of the bet~ ne were used.
Composition of the 1.3 Na20 A1203 o2.9 SiO2 5-1 H20 +
dried pre~ipitation product: 0.1% betaine.
Concentration of the suspension: 9.3% solids having the aboYe co~positlon.
Ca-sequestering 20 power: 116 mg CaO/gm AS.
.
Precipitation: As in Example Zl, except that 1 gm of a betaine ha~ing the ~ormula R - N~ - CH2 COO~
/ \
~ CH3 CH2 ~
wher~in R is coconut alkyl (C12 to C~-alkyl, average chain length C13 5) was used.
Composition of the` 1.3 Na20 o A1203 ~.8 SiO2 o 5.2H20 +
dried precipitation 30 product: 0.05~ betai~e.
Concentration of the suspension: 9.4% solids ha~ing the above composition.
Ca-sequestering power: 106 ~g CaO/gm AS.
- 3~
~OS03~4 ~ MPLE Z5 .
Precipitation: As in Example Zl, except that 1 gm of a b~taine having the iormula .... .
R - ~9 N - CH2 - COO ~3 wherein R is. coconut alkyl, was used Composition o~ the 1.3 Na20 A1203 2-7 SiO2 5-4 H20 *
dried precipitation product: 0.05% betaine.
Concentration of the suspension: 9.4% solids haYtng the abo~e compo~ition.
Ca-sequestering power: 107 mg CaO/gm AS.
. ~XAMP~E Z6 -Precip~tation: As in ~xample Zl, except that 1 gm of a betaine having the ~ormula C12H25 ~ CH2 - COO
N ~ , CH2 ~H2 was used, Composition of the 1.3 Na20 ~ A1203 2.8 SiO~ 5.1 H20 dried precipitation product: 0.05% betaine.
Concentration of the suspension: 9.5% solids ha~ing the above composition.
Ca-sequester~ng power: 110 mg Cao/gm AS.
3~
Precipitation: As in Examp].e Zl, except th~t 1 gm o~
a sul~obetaine having the ~ormula ~12H25 ~ N \ - ~H2 - CH2 - CH2 - so3~3 was used.
Compos~tion o~ the 1~2 Na20 A1203 ~ 2.8 SiO2 ~ 5-1 ~2 dried precipitation product: 0005% sul~obet~ine.
Concentration of the suspension: 9.5% ~ol~ds having the above eomposition.
Ca-sequestering power: 107 mg CaO/gm AS.
EXAMP$E Z8 ~ . .
Precipitation: As ln Example Zl except that 1 gm of a ~ul~obetaine havlng the formula C16~33 - N ~ - CH2 - C~O~ - CH20 - S03~3 ~3 CH3 W2~ used.
Composition o~ the 1.3 Na20 A1203 2-7 SiV2 5-4 H20 dried precipitation product: 0~05~ sulfobetaine.
Concentration o~
the susp2nsion: 9.4% solids ha~ing the abo~e ~omposition.
Ca-sequestering power: 105 mg aO/g~ AS.
1~5V384 Precipi-ta-tion: 50 mg o:F the betaine according to Example Zl in the form of a 30% technical solution and 148 gm of a 35% aqueous solution of Na2O . 3.46 SiO2 were dis-solved in 637 gm of deionized water.
This solution was treated with a solution of 54.8 gm of sodium aluminate (41%
Na20; 54% A1203) in 160 gm of water.
Composition of,the 1.25 Na20 . A1203 2-75 Si02 4 H2O~
dried precipitation product: 0.05% betaine.
Concen-tration of the suspension: About 10% solids having the above composition.
Ca-sequestering power: 100 mg CaO/gm AS.
In order that the very low be-taine content in the precipitation products, especially in that of Example Z9 could be determined with sufficient exactness, the quantity of substance obtained in three batches was extracted with alcohol and freed from inorganic constituents by passage through ion exchange columns. The filtrate was evaporated.
Comparative Test ~i'th R'e'fe'ren'c'e t'o Examples Zl to Z9 Preclpitation: As in Example Al, without the addition of the zwitterionic surfactant.
Composition of the 1.2 Na2O . A12O3 . 2.8 Si02 . 5.3 H20 dried precipitation product: 0.00% surfactant.
Concentration of 30 the suspension: 9.1% solids having the above composition.
Ca-sequestering power 90 mg CaO/gm AS.
~OS0384 A comparison with the suspensions prepared accord-ing to Examples Z1 -to Z9 shows -that in -the comparative -test conducted at 25C, it -takes only one hour until about 95% of the solids settle out at the bottom of the measuring vessel whereas even after 24 hours, less than 10% of -the suspended matter of the suspensions prepared according to -the invention had settled out at the bottom.
As the Examples show, the composition of the pro-ducts according to -the invention lies in -the range of 0.9 to 1.5 Cat2/nO . A1203 . 1.3 to 4 SiO2, where the water con-tent is no-t taken into account. The surfactant content of the products dried in the above-described manner lies between 0.01% to 35%, preferably 0.1% to 20% by weight so far as anionic or cationic surface-active compounds are concerned.
Amounts of 0.01% to 0.1% by ~eight of zwitterionic surface-active compounds ~ere found when the above-described method of determination was used.
One can vary the process described in the Examples by pouring both solu~ons simultaneously into the reaction vessel, In the presence of surfactants resistant to hard-ness, the crystallizability of the sodium aluminum silica-tes is less than that of the sodium aluminosilicates prepared in the usual manner, i.e.,in the absence of surfactants.
Therefore, the products prepared according to the directions given in the Examples remain longer or permanently in an x-ray amorphous state.
105038~
The preceding spsci~ic embodiments are illustrative o~ the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art, or disclosed herein3 may be employed without departing from the spirit of the in~ention and the scope o~ the appended claimæ.
~ 41 -~ 1~72~ 77~ 848 - NI~Jr/gk en~rli~3r-~ DISC~S~
In the principal disclosure aluminosilicates are prepared in the presence of ionic surfactants resistant to the - action ~f water hardness ~ormers such as anionic~ cationic, or zwi~terionie water-soluble organic sur~ace-active compounds.
Pre~erably, however, the cationic surface-active compounds are employed in the production o~ the aluminosilicates o~ the invention When the cationic surfactants are employed, . . .
it is believed they occupy sites within the structural framework o~ the aluminosilicates and supply a controlled release o~ cati-onic sur~actant into the wash solution with improved wash results.
-~2-~ ' ~ ~ .
~3t5~L
EX~LES OF WASHING PERFORMANCE
The following alumlnosilicates were used:
A) An amorphous aluminosilica-te according to the invention (This aluminosilicate contains 2.9% by weight of cationic surfactant within its structural framework.) B) A conventional amorphous aluminosilicate. (This alu~-inosilicate contai~s 3.1% b~ weight of cationic sur-factant adsorbed onto its surface.) Preparation of the aluminosilicates ~ and B:
.
A) 12 gm of hexadecyl-trimethylammonium chloride (25% by weight aqueous solu.ion) were diluted with 633 gm of deionizea water. Then, 148 gm of sodium silicate solution (35% by weight, molar ratio SiO2/~a2O - 3.4} were added while stirring. Following ~his addition, a freshly prepared solu-tion of 54.8 gm o~ sodium aluminate (Na2O/~12O3 = 1.2~
dissolved in 160 ~m of deionized wa-ter was added while con-- tinuing stirring. A suspension of the amorphous surfactan~- ~
modified sodium aluminosilicate was formed.
After -three hours of continued s-tirring, the pre-cipitate was separated by suction fil-tration, washed four times with 50 ml of deionized wa-ter and dried at 70~C for 24 hours. The dried product had the following composition-0.95 Na2O A123 2.4 SiO2 4.4 H2O
!
Surfactant conten-t - 2.9% by weight. - ~
-~3-B
lq~S~31~
B~ 148 gm of sodium silicate solution (same as under A) ¦ were diluted wi~h 637 gm of deionized water. Then while - stirringl 54.8 gm of sodium aluminate (same as under A) dis-solved in 160 gm of deionized wa-ter were added. Tne fo~med S suspension of the amorphous sodium aluminosilicate was stirred ~or three hours. Then, the precipitate was separated by suction fi~-tration, washed four times with 50 ml o deionized water and dried at 70C -Eor 24 hours.
100 gm of the dried amorphous sodium aluminosilicate were suspended in a solution of 20 gm of hexadecyl trimethyl-am~onium chloride (25% by weight aqueous.solution) in 180 gm of deionized water. After stirring for three hours, the solids were separated by suction filtration and dried fox 24 hours at 70C.
The dried product had the following composition:
_ 0.95 Na~O ~12O3 2.5 SiO2 4.5 H2O
Surfactant content = 3.1% by weight.
(The difference of the surfactant content of 0.2%
b~ weight between products A and B was believed to be immaterial.) The washing performance of products ~ and B, respectively, was tested in the following manner:
The sodium aluminosilicate was added to the wash liquor at a dosage level of 2.4 gm of active substance per liter in the presence of 7 ~m per liter of the ~ollowing j liquid laundry de-tergen-t formulations:
~3 .. . .. . . ...
~05~384 Formulation ~
Percent by Weiyht ¦ Alkyl benzene sulfonate, sodium salt 6.4 The condensation product of a hydro-genated tallow alcohol with 5 mols of ethylene oxide per mol of alcohol 2~2 Soap 3~
Sodium silicate 3.0 Sodium perborate 26.5 - .
Magnesium silicate ~.0 Sodium tripolyphosphate 3.0 Sodium citrate 3.0 Sodium sulfate 4.0 EDTA 0.2 Residue water up to 100 Formulation II
. Same as Formulation I, but the alkyl benæene sulfonate was replaced b~ the condensation product o~ a hydrogenated tallow alcohol with 14 mols of ethylene oxide pex mol of the alcohol.
The tests were carried out in the L~underometer at a ratio of water/textile equal to 12:1, using water of 16d hardness at 60C and a duration of 15 minutes. ~11 tests were carried out with both formulations using standard-ized soiled textiles (unfinished cotton, resin finishedcotton, pol~esterJcotton).
The experimental results are summarized in Table 1.
-45- ~
E~ ' .
~5~384 T A B L E
! Remiss;on Data Obtained , _ I , Product Unfinished Resin Fin- Polyester. Cotton ished Co-tton Cot-ton _ _ _ I II I II I II
A Invention 60 62 68 76 53 59 B Non-inven- .
tion 54 64 63.5 72 49 57 The results obtained clearly show the superioxity of the product according to the invention. These results show a bet-ter washing performance of the products according to the invention as com~ared wi ~ dried aluminosilicates post---treated wi~h an aqueous solution of surfactant having the.
same or evën a slightly higher amount of surfactant adsorbed onto the surface of the aluminosilicate particles. : -E ~ ~LE TO RELEASE OF SURF~CTA~T
Products C and D were employed, which were prepared similarly as Products A and B of the previous example.
- ~C) An amorphous aluminosilicate according -to -the invention containing 4.7% by weight of cationic surfactant ~i-thin i-ts structural framework ~D) A conventional amorphous aluminosilicate containing 2.8% by weight of cationic surfactant adsor~ed onto its surface.
-46- ' .. ~.... .. .. .. . . . .... " .. .. .. .... ... . . . .
Two-gram samples of the products wer~ treated at room ~emperature with 100 ml of the following liquids for periods of one hour:
a) distilled wa-ter b) water of 16d (German hardness degrees) c) water of 16d, additionally containing 0.1 mol o Na2SO4 per liter.
After treatmentr the mother liquor was separated by suction filtra-tion and the cationic surEactant content of the mother liquor was determined by reverse Epton-titra-~ - tion. Table 2 shows -the cationic surfactant contents observed in the various experiments.
T ~ B L E 2 - 'i .. . -- Reverse Ep-ton-Titration ~g Cationic Surfactant .
a) Distilled water C 5.1 (invention) -- ~ 6.4 (non-invention) b) 16d water C 6.4 (invention) D 5,1 (non-invention~
c) 16d water ~
0.1 mol/l Na2SO4 C 3.8 (invention) D 2.6 (non-invention) i -47- ~r ~' ' ' .
;
~5038~
The results show that increasing the ionic content~
¦ of the trea-tment solution strongly favors the release of the cationic surfactant from the aluminosilicates of the inven-tion relative -to the release of cationic surfactants, wnich 5 have been adsorbed onto previously made and dried alumino-silicates.
The ratio cationic surfactant released by C divided by the cationic surfactant released by D has the following trend:
a) 5,1:6.4 b) 6.4:5~1 c) 3.8:2.6 0.8 1.~5 1~46 We believe that in the case of the aluminosilicates of the invention, the cationic surfactants occupy si-tes within the structural frame, which can also be occupied by sodium ions. Therefore, there will be a competition between .
cationic.surfactants and sodium ions for these sites. A
reoccupation of these sites by the surfactant is less li~ely i~ competing sodium ions are around. Therefore, a relative - increase in the ra-te of surfactant release is observed in the case of aluminosilicates of the invention in the presence of sodium ions.
B
~ Y 13 II) R3 - ~ N _ R5- N ~4 ~ X
- Rl - Rl ,, l3 III) R6 ~ ~ i ~ R5 - ~ X
Z ~2 .
In these formulae~
~1 is an aliphatic, cycloal~phatic, or alkyla~omatic group having 10 to 22 carbon atoms, prefe~ably a straight-chain alkyl group having 12 to 22 carbon atoms, R2 is an alkyl group having 1 to 4 c~rbon at~ms, or an alkylol group having 2 to 4 carbon atoms, or a polyether residue havin~ the formula - ( CH2-CH2-0) m~H
in which m = 2 to 5, R3 i~ the group R2 or a phenyl, ben~yl or toluyl group, R~ is an alkylene group or a hydroxyalkylene group - having 2 to 4 carbon atom~, R5 is an alkylene group ha~ 2 to 4 carbon atoms~
R6 is a saturated or ethylenically-unsaturated, pre~
~erably stralght-ch~in hydrocarbon ~esidue ha~lng , .
. 9 to 21, especially 11 to 17 carbon atoms~
~6~3~
X are the groups -C00~, -0-S03-, or -S03-, Y are the groups H or X, Z are the grollps H or R2, and n is an integ~r ~rom 1 tlD 100.
Betaine~ ha~ing the fo:rmula I are prepared by cau~ing tertiary amine of the ~o:rmllla RlR2R3N to react with halocarboxylic a6ids, for ~xample, chloroacetic acid, bromo-acetic acid, or a-chloropropionle acid, or b~ quaternizing in suitable Dlanner aninocarboxylic acids or the product of the react~:on o~ secondary amine~ with acrylic acld. Sul~ate betaines are analogou~ly obtainable by the react3~on oi the tertlary ~m~ne 8 with the e ~ters or ~alt~ ~ haloalkylsul~uric acids. Sul:eobetaines are obtainable by the reaction of the tertiary amine~ ~ith haloalkylsulf`onic acids or sulto~es3 e~pec~ally wlth propane~ultone.
Formula II includes example. ~or compound~ having ~everal betaineg sul~ate-betaine, or ~ul:eobet~lne grou~
To prepare these compounds, polyethyleneimin2, polypropylen~
imine, or polybutylenimine are alkyla ed, and then reacted in the above-mentioned manner with halocarboxylic acid~, haloalkyl~uliuric ac~d esters, haloal~ylsul:fonic acid~ or sultones. Alternativ~ly, the polyethylenelmineæ can be ~ir~t ca~sed to react with acrylic acid derivatives and then be alkylat~d by introduction o~ the gro~p Pcl. Compounds o~ the i~ormula III can be obtaincd when natural or synthetic ~atty acid~ are condensed ~ith ethylenediamine, N-alkyl-ethylenediamine or N-hydroxyalkylethylened:iamine, ~ollowed by reaction ~rith halocarboxyli~ acids, haloalkylsul~uric acid ester~ or haloalkyl~ul:eonic acids or sultone~. In addl-tion to the above methods o:P preparation, other methods 3~g~
can be u~ed, ~or example, the reactlon of te~tiary amines ~ith epichlorohydrin, ~ollowed by the introduction of sul~ate or sul~onate groups.
~ xamples of these zwittlerionic sur~ace-active com-pounds are:
N-alkyl-N-dim~thyl-am~onium-methyl carboxylate, N-alkyl-N-benzyl-N-methylammonium-methyl carboxylate, N-alkyl~N-bis-(2-hydroxyethyl)-ammonium-methyl carboxylate, N-alkyl-N-diethylammonium-ethyl carboxylate~
2-alkyl-1-(~-hydroxyethyl)-imidazollnium-1-methyl carboxylate, 3-(N-alkyl-N-dim~thylammonium)-2-hydroxypropyl-sul~ate, 3-(N-alkyl-N-dimethylammonium)-propane-sulfon~te, and 1-(3-trim~th~lammonium)-alkane-sulfonate, in which the alkyl or the alkane group~ preferably are long-chain hydrocarbon re~id~es having 10 to 22~ pre~erably 12 to 18, carbon atoms and can be, ~or example, derived ~rom natural ~atty re~idues, such a~ are obtainable from coconut oil or tallow.
In the ne~ compounds, the urfactants c~n be Bound to the sur~ace of the aluminosilicate particles, but they can be also embedded in the alumina~llcates. In mo~t case~, they are adsorbed on the surface as w~ll a~ embedded in the aluminosilicate~
Surfactant~ havlng bulky hydrophobic res~due~ (for example, sueh a~ ~rith branched chain~ or ring ~ystem~) have been æhown to be more solidly anehored in the new compound~
than those having straight-chain aliphatic residue~. The latter ~ur~actant~ are easier dissolved out ~rom the alumino_ silicate than the f ormer when the new compounds vr their 30 suspensions are introduced into water.
_ 14 -~ ~5~D3 8 ~
Of special in~erest are the new compound~ which have been prepared ~rom cationic or zwitterionic surf`actants whlch likewi~e can be ~ound to the surface o~ the alumino-~ilicates. They can be also embedded in the aluminosilicate~.
In most cases, e~pecially the catLonic surfactants ~re not on~y adsorbed on ~he sur~acs (i.e., they ~orm a part of the previously mentioned cation "Cat" when the compo~ition of the aluminosil~cate~ was di~cuæsed), but they are al~o embe~ded ln ths alumino~llicates.
In aqueou~ solution, the new sur~actant-containing alumlnosilicate ~ub~tances relea~e the bound ~urf~ctants.
m erefore, the types charged ~ith anionic or zwit~erionlc ~ur~actants are suitable as additives to washing and cleaning liquors. The alumlnosilicates charged ~ith cationic surfac-tants are distinguished by a remarkable adsorption power for d~ssolved dye~tu~s or d~spersed pigments, hence can be used as adsorpti~e agents ~or such substanc~s. In case the catlonic sur~actants ha~e antimicrobial properties, the new compounds can be used wherever a gradual release of the cationic ~ur 20 ~actants to the ~urrounding liquid is de~ired.
The ~ollo~ing example~ are illustrative of the pr~Lctice of the invent~on ~ thout being limitati~ o~ the ~ame in any respect.
E X A M P L E S
The ~urI actant-containing alumino~ilicates o~ the in~entit)n are manuL~actured accordi ng to the following dlrec-tions unleæs ~nother m~thod of operation i~ expre~ly stated.
A solution o~ the surfa~a-active compound ( sur~ac-tant) and an alkali metal silicate in deioni~ed water was l~SO3l~4 introduced into a one-liter vessel and while mixing wi-th a high-speed intensive stirrer (10,000 rpm, "Ultraturrax", made by Janke ~ Kunkel IKA-Werk, Stauffen/Breisgau, Germany), the aluminate solut~n was then added in small portions.
Immediately before use, the solu-tion of Na20 . 8 SiO2 had been prepared from finely divided, easily alkaline-soluble silicic acid and commercial water glass. After stirring had been continued for 30 minutes, an alîquo-t part of the alumino-silicate suspension which had been formed was separated for isolating the aluminosilicate. For this purpose, the solution was filtered with suction from the solid which had been formed, and the residue on the filter was washed with deionized water.
The residue on -the filter was dried a-t 80C for -three hours under 100 mm Hg pressure and then analyzed. The yields of the products thus dried amounted to 70% to 95% of the theore-tical.
The water content was determined with Fischer's reagent and for the determination of the amount of the anionic or cationic surfactants, 0.5 gm of the new product were dissolved in 50 ml of lN H2S04 at boiling, followed by titration of the surfactant according to Reid et al, "Tenside", Vol. 4 (1967), pp. 292-304. For the determination of the zwitterionic surfactants, the DGF Standard Method H III 4 (65) was employed. (DGF-Einheitsmethoden, S-tuttgart, 1969 --DGF ~ Deutsche Gesellschaf-t fur Fettwissenschaften, German Society for the Science of Fats.) All data given in % are percent by weight. The contents of surfactants are based on the precipitation pro-duct which has been dried in the above-described manner and still contains bound water. If these contents were to be ~0~)384 computed on the basis o~ the m$xture o~sur~actant and anhy-drous inorganic active su~stance, somewhat h~.gher values would be obtainPd.
Comparative substances were p~ pared under the same conditi~ns, e~cept that sur~aetants were omitted from the startlng solutions. These compo~lds and the compounds ~ the invention were compared in the determination of the Ca~eques-tering power according to the fol:Lo~ing method:
One gram o~ the product dried in the above_de3cribed manner (on an AS basis) was stirred a~ 50C for 15 minutes with one liter of a solution of 0.7~65 gm o~ CaC12 2 H20/
liter (equal to 30 dH - German hardneæs) which had bee:n ad,~usted to a pH o~ 10. A~ter the ælum~n7lm silicate ha~ been filtered of~, the resldual hardness "x" of the ~il1;rate was determine~ from which the Ca-sequesterlng power ~as computed in mg CaO/gm AS according to the iormula: (30-~) . 10.
The sur~actants which were used, the anlonic sur-~ace-active compounds or anionic sur~actants being present a~
Na-salts, were designated b~ the following abbreviat~ons:
2C "ABS" desi~nate~ the salt of an alky~benzene-sul~onic ac~d having 10 to 15, pre~erably 11 to 13~
carbon atoms in the alkyl ~hain, ~ich acid had been prepared by the cond~n~atlon of straight-chaln olefins with ~enzene, followed by sulionation o~ the al~
benzene thus formed~
"TPS" designate~ the salt of an alk;ylbenzene-sul:Eonic acid having 9 to 15, pre~erably 12, carbon atoms in ~e alkyl chainl whlch acid had been prepared by the cond2nsation o~ technical tetraprop~lene with benzene, ~ollowed by sul~onation of the alkylbenzene thus ~ormed.
~0 ~ 3 ~ ~
"MS" des~gnate~ the salt of a mixture of alkanemono-~ulfonates and alkanedisulfonates ~"Mersolat"), which mixture has been prepared by sulfochlorination o~ a C12_~8-par~rfin~ saponi~icat,ion o~ the sulfochloride thus formed with aqueous sodium hydroxide and separation o~ the non-converted paraffin mixture from the sulfonate~
"FAS" designates the sulfate of dodecyl alcohol.
"FA-E0-S" designates the sulfate of an adduct of two mols of ethylene oxide with one mol o~ a fatty alcohol derived from coconut oil.
"OS" designates a sulfonate th~t has been preparea ~rom a-ole~in mixtures having 15 to 18 carbon atoms by sul~onation with S03 and hydrolysis o~ the sulfonation product with aqueous sodium hydroxîàe, whlch sulfonate essentially consists of alkenesul~ona~e and hydroxy-alkanesulfonate and which, in addition, contains small quantitie s of` alkanedi sulf on~te s .
"FA-E0-C~" designates the carboxymethyl ether of an adduct of 4.5 mols of ethylene oxide with one mol of a ~atty alcohol derived ~rom coconut oil.
"CTMA" - ce~yltrimethylammonium chloride . "CTMB" = cetyltrimethylammonium bromide "~TMA" = lauryltrimethylammonium chloride "~YPC" = laurylpyridinium chloride "L~DM" - laurylbenzyldi~.~ethylammonium chloride '9~DBD" = lauryl(d~chlorobenzyl)dimethylammonium chloride "TDM~" = dl-(palmityl/stearyl)-di~ethylammoniu~
chloride, where the palmityl/ste~ryl alkyl mixture is d~ri.ved ~rom tallow ratty acids.
1~ ~ 3 EXAMPLE Al __ Precipitation: 0.5 gm o~ ABS in the ~orm o~ a 20%
technical solution and 90.4 gm o~ a 25~ aqueous ~olution of Na20 ~ 8 SiO2 dissolved in 300 ml o~ deionized water were precipltated wlth a ~olut~on o~
27.L~ gm of sodium aluminate (41~ Na20, 54~ A1203) in 80 ml o~ water.
Composition of the 1.3 Na20 A1203 2-9 SiO2 5-1 H20,dried precipltatioh product: 009% A~S.
Concentration of the su~pension: 9.1% solids having the above compo~ition.
Ca-seq~estering po~r: 110 mg CaO/gm AS.
~XAMPIæ A2 Precipitation: As in ~xample Al, except thRt 1.0 gm oi AB~ wa~oused.
Compositlon o~ the 1.2 Na20 A1203 2~8 SiO2 ~ 6.4 H20, dried precipitation product: 1.5% ABS.
Concentration o~
the ~uspension: 9.5~ soli as ha~ing the above composition.
Ca-sequestering power: 109 m~ CaO/gm AS.
Precipitation: As in ~xample Al, except that 2.5 gm of ABS were u~ed.
Composition of the 1.2 Na20 A1203 2.9 S102 ~.B H20, dried precipitation product: 3.5% ABS.
Concentration of the suspension: 9.3% solias having the above composit~on, Ca-sequestering power: 114 mg CaO/~m AS.
- 19 ~
~L6gS~3~9~
Precip~tation: As in Example Al~ except that 5 gm of ABS were u~ed.
Composition of the 1.2 Na20 ~ A1203 2.9 SiO2 4-2 H20, dried precipitation product: 6~3% ABS
Concentration o~
the suspension: 9.4% 301id~ havlng the abo~e composltion.
Ca-s~questering power: 107 mg CaO/gm AS.
EXAMPLEA~
Precipitation: As in ~xampls Alg except that 10 gm of ABS ~ere u~ed.
Composition of the 1.2 Na20 A1203 3.2 SiO2 6.3 H20, dried precipitation product: 1105~ ABS.
Concentration of the suspension: 10.2~ solids ha~ing the above composition.
Ca-sequestering power: 110 mg CaO/gm AS.
Precipitation: As in ~xample Al, except that 50 gm o~
ABS were used.
Composition of the 1.3 Na20 Al2o3 2-7siO2 ~ 3 9 ~2 dried precipitation product: 33.4% ABS.
Concentration of the suspension: 11.7~ solids having the abo~e composition.
Ca-sequestering power: 105 mg CaO/gm AS.
_ 20 -5~31~
~XAMPLE A7 Precipitation: A~ in ~xample Al, except that 1 gm of TPS wa~ used in the ~orm of a ~olution containing 20 gm/liter.
Composition of the 1.2 Na~O A1203 2-a S102 ~-4 H20, dried precipitation product: 1.7~ TPS.
Concentration of the su~pension: 9.5~ solids having the above composition.
Ca-sequestering - power: 108 mg CaO/gm A~.
, Precipltation: As in Ex~mple Al, exc~pt that 1 gm of MS
was used in the form o~ a solution con-taining 20 gm~liter.
Composition of the 1.1 Na20 A1203 2.7 SiO~ 4.1 H20 , dried precipitation product: 0.1% MS.
Concentration of the suspension: 8.9% solids ha~ing the abo~e composition.
Ca-sequestering power: 104 mg GaO/gm AS.
EXAMPL~ A9 Precipitation: As in ~xample Al, except that 1 gm of FAS was used in the form of a ~olution containing 20 ~m/liter~
Composition of the 1.2 Na20 A1203 ~ ~.9SiO2 6.4H~o, dried precipitation product: 0.1% FAS.
Concentration of the suspension: 9.3~ solids having the abo~e composition, Ca-sequesterlng po~er: 111 mg CaO/gm AS.
:1~5~3~34 ~XAMPLE A10 __ Precipitation: As in Example Al, except th~t 1 gm of Fa-~O-S wa~ ueed in the iorm o~ a solutiom containing 20 gm/liter, Composition of the 1.2 Na20 A1203 . 2-9 SiO2 6-1 H20, dried precipitation product: 0.1% Fa-~O-S.
Concentration of the suspension: 9.3~ solids having the abov~ composition.
Ca-æequestering power: 120 mg Cao/gm AS.
EXAMPLE All Precipitation: As in ~xample Al~ ~xcapt that 1 gm o~ OS
was u~ed in the form of a solution con-taining 10 gm/liter~
Composition o~ the 1.2 Na20 A1203 2.8 SiO2 6~7 H20, dried precipitation product~ 0.1% OS.
Concentration of the suspension: 9.~% solids having the above composition.
Ca-sequestering power: . 108 mg CaO/gm AS.
Precipitation: As in Exa~ple Al, ~xcept that 1 gm o~
Fa-~O-CME wa~ uæed.
Composition o~ the 1,2 Na20 A1~03 2.9 SiO2 5-3 H20, dried precipitation product: 0.2~ Fa-EO-CME.
Concentration of the suspension: 9.1% solids ha~in~ the above composition.
ca-sequestPring power: 98 mg CaO/gm AS.
~5~33~4 _omparison Test_with Re~erence to Examples Al to A12 ~recipitation: As in Example Al, except that no sur-factant was used.
Composition of the 1.2 Na20 A1203 2.8 SiO~ 5.3 H?0, dried precipitation product: 0.00~ surfactant.
Co~centration of the suspension: 9.1~ solids having the above compositio~.
Ca-sequestering power: 90 mg Cao/gm AS.
When the products according to Examples Al to A12 were compared with the product of the comparative test, with reference to the stability o~ the a~ueous suspensions, this comparison shows that the sedimentation rate in the product of the comparative test is considerably higher, which means that the products according to the ~nvention can be held for a longer period of time without depositing sediment. Further-more, the products according to the lnvention show a higher cation exchange capacity than the products without the addition of surfactants.
~.
~L~5038~
Precipitation: 0.1 ~m o~ ABS in the form of a technical 20% solution and 9.05 gm o~ a 25% aque-ous solution of Na20 8 SiO2 d~ssolved in 400 ml of deionized water were reacted ~lth a solution of 5.50 gm o~ sodium aluminate (41~ Na20; 54~ A123) in 80 ml of water.
Composition of the 1-2 Na2 A1203 0 2-7 SiO~ 6.4 ~2-dried precipitation product: 0.7% ABS.
Concentration o~
the ~uspension: About 2~ æolids ha~ing the abo~e compo3ition..
Ca-sequestering power: 105 mg Cao/gm AS.
Precipitation: 4 gm o~ ABS in the form of a 20~ tsch-nical solution were dissolved in 10 ml of deionized water and mixed with 361.6 gm of a 25% solution o~ Na20 -8 SiO2. To th~s solution~ 10906 gm o~
solid sodium aluminate (41% Na~0, 54~
A1203) were added in proportions while stirring vigorously.
Composition of the 1.2 ~a20 A1203 2.7 SiO2 5.1 ~2 dried precîpitation product: 2~ ABS.
Concentration of the suspension: 37.2% solids having the above composition.
Ca-sequestering power: 98 mg Cao/gm AS.
- 24 - ~
~L~5~384~
.
Precipitation: 1~0 gm o~ ABS in the ~orm of a 20%
technical solution and 32.6 gm of soaium aluminate (41% Na20; 54% A123) were di~solYed in 300 ml of deionized water.
The solut1on was treated wlth 70 gm of a 25% Na20 8 SiO2 solution ln 100 ml o~ wat~rO
Composition of the 1~1 Na20 A1203 1.6 SiO~ 4.8 H209 dried precipitation product: 1.6~ ABS.
Concentration of - the suspension: 9. 2% solids ha~ing the abo~e composition.
Ca-s~questering power: 115 mg CaO/gm AS.
Precipitatinn: 1.0 gm o~ ABS in the form of a 20%
technical solution and 18.8 gm o~
sodium alumlnate (41~ Na20; 54~ A1~03) were dissolved in 300 ml of deionized water, This solution was treated with a ~olutlon o~ 124.5 ~m of a 25% solu-tion o~ Na20 8 SiO2 in 100 ml of . -water.
Composition of the 1.5 Na20 A1203 3-~si02 5-2 H20 3 dried precipitation product: 1.7~ ABS.
Concentration of the suspension: 9.9~ solids ha~ing the abo~e composition.
Ca-sequestering power: 116 mg CaO/gm AS.
- 25 -.
~95~313~
Precipitation: 0.1 gm o~ AB~ in the form of a 50%
technical paste and 148 gm o~ a 35%
aqueous solution of Na20 3 . 46 SiO2 dis~ol~red ii~ 637 gm deionized water w~re treated w~th a solution of 54~8 gm o~ sodium aluminate (41~6 Na20; 54%
- A1203 ) in 160 gm of water .
Composition of the 1.25 Na20 A1203 2-75si02 4 H2 dried precipitation product: . 0.032~ ABS.
Concentration of the suspension:. About 10% solids ha~ing the above composition.
Ca-sequestering - ~ower: 100 mg CaO/gm As.
In order that the low content of surfactant in the precipitation product according to Example A17 could be determined with sufficient accuracy, the amount o~ substance ~b~ained in three batches was extracted with alcohol, and the solution thus obtained was concentrated and titrated as described above.
?
~S~;!1384 EXAMPLE Kl Precipitation: 0.5 gm o~ CTMA i~ the Porm of a 25 technical solutlon and 90.4 gm of a 25~ Na20 8 S~02 solution were d~ssolved in 300 ml deionized water. This solution was treated with a solutinn o~ 27.4 gm of sodium aluminatc (41% Na20; 5~%
A1203) in 80 ml of water.
~Composition of the 1.2 Na20 A1203 2o9$i02 6-4H
dried precipitation product: 0.9% CTM~
~oncentration of the suspenslon: 9.4% solidæ having the aboYe composition.
ca-sequestering power: 109 mg CaO/gm A5.
EXAMPL$ K2 Prècipitation: As ln Example Kl, except that 1.0 gm of CTMA was used.
Composition o~ the 1-2 Na2 A1203 2-8 SiO2 6.8 H20, dried precipitation product: l.9~o CTMA.
Concentration of the suspension: 9,~ sollds having the abo~e composit~on.
Ca-sequestering power: 113 mg CaO/gm AS.
~XAMPLE K3 -Precipitation: As in Example Kl, except that 2.5 gm of CTMA ~ere used.
Composition of the 1.1 ~a~o A1203 ~ 3.1 sio2 ~ 5.5 ~2~
dried precipitation product: 4.6% CTMA.
Concentration of the ~uspen~ion: 9. 5% solidæ haYing the above composition.
Ca-sequestering power: 121 mg Cao/gm AS.
~XAMPLE K4 Precipitatlon: As in Exam~le Kl, except that 5 gm Or CTMA w~re u~ed.
Composition of' the 1.3 Na20 A1203 3.2sio2 ~ 5.4 H~O, dried precipitation product: 603% CTMA.
Concentration of the suspension: 9.9~ ~olids having the above composition.
Ca-sequestering power: 114 mg Cao/gm AS~
E MPLE E~
P:recipitation: As in Example Kl, except that 1() gm Or CTMA were used.
.Zomposition oi the 1,2 Na20 A1203 ~ 2.9 SiO2 ~ 4-~ ~2~
dried precipitation product: 15.3~ GT~A.
Concentration of' the suspenslon: 10.8% solids having the abova composltion.
Ca-sequestering power: 128 mg CaO/gm AS.
~1[)5038~
__ Precipitation: A~ in ~xample Kl, except that 50 gm of CTMA ~ere u~ed.
Composition o~ the 1.2 Na20 A1203 2-8 SiO2 5-7 H20 dried precipitation product: 14.3% CTMA.
Concentration of the su~pension: 10~4% solids haYing the above composition.
Ca-sequestering power: 122 mg Cao/gm AS~
.
Precipitation: As in ~xample El9 except that 1 gm of LTMA was u~ed.
Compo~ition o~ the 1.3 Na20 A1203 2-9 SiO2 5-3 H20, dried precipitation product: .1.4~ LTMA.
Concentration o~
the suspension: 9.2% ~olids having the above composition.
Ca-sequestering po~er: 115 mg CaO/gm AS.
~XAMPLEK8 Precipitation: As in Example Kl, except that 1 gm of BPYC wa~ used.
Composition o~ the 1.1 Na20 A1203 2.8 SiO2 ~ 6.5 H20 , dried precipitation product: 1.2~ ~P~C.
Concentration of the suspension: 9.5% solids having the above compositionO
Ca-sequestering power: 107 mg Cao/gm AS.
1051~384 Comparison Test with reference to ~xam~les Kl to K8 Prec~pitation: A~ ln Exampl~ Kl, except that no suriactant Wl16 added.
Composition o~ the 1.2 Na20 A1203 2-8 ~i2 5-3 H20 dsied preclpitation pr~duct: 0.00% ~urfactant Concentration of the ~uspension: 9.1% solids ha~ing the abo~e composition.
. ~a-sequestering 10 po~er: go mg CaO/gm AS.
When the suspensions prepared according to Example~
Kl to K8 were compared with the suspension of the comparative -- test~ this compari~on shows that the latter ~uspension ha a considerably higher s~dimentation rate, which means that - ~ the suspen~ion~ according to the in~ention can be stored -~or a longer period o~ time without deposit~ng sediment.
Precipitation: 0.1 gm o~ CTMA in the ~orm of a 25 . technical solution and 9.05 gm of a 25~
NaO2 8 SiO2 solution were dissolved in 400 ml deionized water. This solution ~as treated with a solution of 5.50 gm of sodium aluminate (41~ NaO2; 54 A1203) in 80 ml of water.
Composition o~ the -1.1 Na20 A1203 2.7 SiO2 5.6 H20 , dried precipitation product: about 2% of CTMA
Concentration of the suspension: 1.8~ solids having the above composition.
Ca-sequestering power: 116 mg CaO/gm AS.
_ 30 -~0503~34 EXAMPL$ K10 .
Precl.pitation: 4 gm of CTMA in the form of a 25% tech-nical solution were dissolved in 10 ml of deionized water and mixed with 361.6 gm o~ a 25% Na20 ~ 8 SiO2 solution.
109.6 gm o~ ~olid ~odium aluminate ~41~ Na20; 54% A1203) were added in:por-tions to this solution while stirring - Yigorously.
Co~position o~ the 1.3 Na20 ~ A1203 . 3-3 SiO2 7-4 H~O, dried precipitat~on product: 1.9% CTMA
~oncentration o~
the suspension: 38.3% solids ha~tng the above compos~tion.
Ca-sequestering p~w~r: 9~ mg CaO/gm AS.
~XAMPLE Kll Precipitation: 1.0 gm of ~TMA in the ~orm of a 25 technical solution and 32.6 gm of sodium aluminate (41~ Na20; 54~ A1203) were dissolved in 300 ml deionized water. This solution was treated with a solution of 70 gm o~ a 25% Na~O 8 SiO2 solutlon in 100 ml of water.
Composition o~ the 1.0 Na20 A1203 1-6 SiO2 5-3 H20, dried precipitation product: 1.5~ CTMA.
Concentration o~
the suspension: 9.2% solids ha~lng the abo~e composition.
Ca-sequestering power: 115 mg CaO/gm AS.
- 31 ~
~XAMP~E K 12 .
Precipitation: 1.0 gm of CTMA *n the form o~ a 25~
technical solution and 18.8 gm of sod~um aluminate (41% Na20, 54~ A1203) were dissolved in 300 ml o~ de~onized water.
This solution wa~ treated with a solution of 124.5 gm of 25~ Na20 8 SiO2 solution in 100 ml o~ water.
Composition o~ the 1.5 Na20 A1203 3.8 SiO~ ~ 5.2 H~O , dried precipitation product: 1.9% CTMA, Concentration o~
the suspension: 9.7~ solid~ ha~ing the above compo~ition.
Ca-sequestering power: 108 mg CaO/gm AS.
E ~
Pre~ipitation: As in Example Kl,.except that 1.0 gm of . LDBD was used.
Composition of the 1-2 Na20 ~ A1203 2-8 SiO2 5-4 H20 dried precipitation product: 1.8% LDBD
Concentration of the suspension: 9.7% ~olids ha~ing the abov~ composition.
Ca-sequestering power: 110 mg Cao/gm AS.
.
Precipitation: As in Example Kl, except that 1.0 gm of 1BDM was used .
Composition of the 1.2 Na20 A1203 2.7 S102 ~ 5.9 H20, dried precipitation product: 1. 7~ ~BDM~
Concentration o~
the suspension: 9.5% ~olids having the abo~e composition.
Ca-sequestering power: 116 mg Cao/gm AS.
~5~384 BXAMPLE Kl~
Precipitation: A~ in ~xample Kl, except that 1.0 gm of TDMA ~as used.
Composition of the 1.2 Na20 A1203 2-8 SiO2 5-7 H20, dried precipitation product~ % TDMA.
Concentration of the suspension: 9.7% solids ha~ng th~ above composition.
Ca-sequestering power: 114 mg Cao/gm AS.
~XAMPLE K16 Precipitation: As in ~xample Kl, except that 1.0 gm of CTMB was used.
Composition o~ the 1.1 Na20 A1203 2.9 SiO2 ~ 4.8 H20, dried precipitation product: 1.9~ CTMB.
Concentration of the suspension: 9~9~ solidæ having the above composition.
Ca-sequestering power: . 108 mg Cao/~m AS.
Precipitation: A~ in ~ample Kl, except that 5 gm of N,N-didodecylamine w~e used in place of the CTMA.
Composition of the 1-37Na20 A1203 2.7 SiO2 ~4018 H20 +
dried precipitation product: 705% N,N-didodecylamine.
Concentrati~n of the suspension: About 10% solids having the abo~e compositlon.
Ca-sequestering power: 115 mg CaO/gm AS.
- 3~ -~05~1138~
~XAMPIE K 18 Precipitatlon: A~ in Example Kl, except that 5 mg of ~-dodecyl-N,N-dimethylamine were u~ed in place of the CTMA.
Sompo~ition of the 1.32 Na20 A:1203 2.57 SiO2 ~ 4.52H20 dried precipitation product: 1.6~ o~ N-dodecyl-N,~-dimethylamine, Concentration o~
~he suspension: About 10% solld~ ha~ng the abo~e compo~ition.
Ca-se~uestering power: 115 mg CaO/gm AS.
EXAMPLE Kl9 __ Precipitation: A~ in Example gl~ except that 5 gm of octylamine were used in place of the CTMA.
Composition of the 1.01 Na20 A1~03 :2~,3-9SiO2 3.87 ~2 +
dried precipitation product: 3.1~ octylamine.
Concentration o~
the suspension: About 10% solids ha~ing the abo~e composltion.
Ca-sequestering power: 110 mg Cao/gm AS.
EXAMP~E K20 Precipitation: As in Example Kl, except that 5 gm o~ a tertiar~ a~lne group containing C12_18 coconut oil fatty acids-polydiethanol_ amide (obbRined as the condensation pro-duct of 1 mol of coconut oil ~atty acid~
and 2 mols of diethanolamine3.were used.
Composition of the 1.36 Na20 A1203 2-38S~02 3~78H20 +
dried pr~cipitation 3 4~ coconut fatty acid-polydiethanOlam Concentration of the suspension: About 10% solids ha~ing the aboYe composition.
Ca-sequestering ~ power: 120 mg CaO/gm As.
- 3~ -~AMPLE K21 iO ~ 3 84 Precipitation: 50 mæ of CTMA i~ the form of a 25~
technical solutlon and 148 gm of a 35%
aqueous solution o~ Na20 3.46 SiO2 were dissol~ed in 637 gm o~ deionized water. This solution was tre~ted with : ~ solution of' 54.8 g~ of sodium alum-~nate (41~ Na2, 54~ A1203) in 160 gm . . of water.
Composition of the 1.25Na20 A1203 ~ 2.75 SiOz 4 H20, dried precipL~a~ion pro~uct: 0.02~ CT~
Concentration of the suspension: About 10~ solids ha~ing the above co~position.
Ca-sequestering power: 100 ~g CaO/gm A5.
.:
In order that the lo~ content o~ sur~ctant in the precipitation product o~ Example K 21 could be datermined with sufficient accuracy, the quantity o~ substanc~ obtaine~
in three batches ~ras extracted ~ith alcohol, and the solutinn th~s obt~ined was.concent~ated and tested as described above.
EXA~P~E Zl Precipitation: - As in Example Al, ~xcept that 1 gm o~
a beta~ne having the formula -C12H~5 j N \ - C~2 - COO
C~3 C~3 was ~dded-to the sodium silicate solutlon . ) in place of the ABS.
Co~position o~ the 1.3 Na20 A1203 2.7 SiO2 5.6 H20 dried precipit2~ion 30 product: 0.05~ betaine. .
Concentration o~
the suspension: 9.4% solids havin8 the above compositicn.
Ca-sequesterin~ .
power: 103mg CaO~gm AS.
, . ~ 35 .
~05~)3~3~
.
Precipitat~on: As ln Example Z1, except that 5 gm of the betaine were used.
eomposition of the 1.2 Na20 ~ A1203 . 208 SiO2 409 H20 dried prec~pitation product: o.o6~ betaine.
Concentration of the suspension e 90 5% sol~d~ having the abo~e composltion.
Ca-sequestering p~wer: 105 n4~ CaO/gm AS.
Precipitation: As in Exampl~ Zl, except that 25.0 gm of the bet~ ne were used.
Composition of the 1.3 Na20 A1203 o2.9 SiO2 5-1 H20 +
dried pre~ipitation product: 0.1% betaine.
Concentration of the suspension: 9.3% solids having the aboYe co~positlon.
Ca-sequestering 20 power: 116 mg CaO/gm AS.
.
Precipitation: As in Example Zl, except that 1 gm of a betaine ha~ing the ~ormula R - N~ - CH2 COO~
/ \
~ CH3 CH2 ~
wher~in R is coconut alkyl (C12 to C~-alkyl, average chain length C13 5) was used.
Composition of the` 1.3 Na20 o A1203 ~.8 SiO2 o 5.2H20 +
dried precipitation 30 product: 0.05~ betai~e.
Concentration of the suspension: 9.4% solids ha~ing the above composition.
Ca-sequestering power: 106 ~g CaO/gm AS.
- 3~
~OS03~4 ~ MPLE Z5 .
Precipitation: As in Example Zl, except that 1 gm of a b~taine having the iormula .... .
R - ~9 N - CH2 - COO ~3 wherein R is. coconut alkyl, was used Composition o~ the 1.3 Na20 A1203 2-7 SiO2 5-4 H20 *
dried precipitation product: 0.05% betaine.
Concentration of the suspension: 9.4% solids haYtng the abo~e compo~ition.
Ca-sequestering power: 107 mg CaO/gm AS.
. ~XAMP~E Z6 -Precip~tation: As in ~xample Zl, except that 1 gm of a betaine having the ~ormula C12H25 ~ CH2 - COO
N ~ , CH2 ~H2 was used, Composition of the 1.3 Na20 ~ A1203 2.8 SiO~ 5.1 H20 dried precipitation product: 0.05% betaine.
Concentration of the suspension: 9.5% solids ha~ing the above composition.
Ca-sequester~ng power: 110 mg Cao/gm AS.
3~
Precipitation: As in Examp].e Zl, except th~t 1 gm o~
a sul~obetaine having the ~ormula ~12H25 ~ N \ - ~H2 - CH2 - CH2 - so3~3 was used.
Compos~tion o~ the 1~2 Na20 A1203 ~ 2.8 SiO2 ~ 5-1 ~2 dried precipitation product: 0005% sul~obet~ine.
Concentration of the suspension: 9.5% ~ol~ds having the above eomposition.
Ca-sequestering power: 107 mg CaO/gm AS.
EXAMP$E Z8 ~ . .
Precipitation: As ln Example Zl except that 1 gm of a ~ul~obetaine havlng the formula C16~33 - N ~ - CH2 - C~O~ - CH20 - S03~3 ~3 CH3 W2~ used.
Composition o~ the 1.3 Na20 A1203 2-7 SiV2 5-4 H20 dried precipitation product: 0~05~ sulfobetaine.
Concentration o~
the susp2nsion: 9.4% solids ha~ing the abo~e ~omposition.
Ca-sequestering power: 105 mg aO/g~ AS.
1~5V384 Precipi-ta-tion: 50 mg o:F the betaine according to Example Zl in the form of a 30% technical solution and 148 gm of a 35% aqueous solution of Na2O . 3.46 SiO2 were dis-solved in 637 gm of deionized water.
This solution was treated with a solution of 54.8 gm of sodium aluminate (41%
Na20; 54% A1203) in 160 gm of water.
Composition of,the 1.25 Na20 . A1203 2-75 Si02 4 H2O~
dried precipitation product: 0.05% betaine.
Concen-tration of the suspension: About 10% solids having the above composition.
Ca-sequestering power: 100 mg CaO/gm AS.
In order that the very low be-taine content in the precipitation products, especially in that of Example Z9 could be determined with sufficient exactness, the quantity of substance obtained in three batches was extracted with alcohol and freed from inorganic constituents by passage through ion exchange columns. The filtrate was evaporated.
Comparative Test ~i'th R'e'fe'ren'c'e t'o Examples Zl to Z9 Preclpitation: As in Example Al, without the addition of the zwitterionic surfactant.
Composition of the 1.2 Na2O . A12O3 . 2.8 Si02 . 5.3 H20 dried precipitation product: 0.00% surfactant.
Concentration of 30 the suspension: 9.1% solids having the above composition.
Ca-sequestering power 90 mg CaO/gm AS.
~OS0384 A comparison with the suspensions prepared accord-ing to Examples Z1 -to Z9 shows -that in -the comparative -test conducted at 25C, it -takes only one hour until about 95% of the solids settle out at the bottom of the measuring vessel whereas even after 24 hours, less than 10% of -the suspended matter of the suspensions prepared according to -the invention had settled out at the bottom.
As the Examples show, the composition of the pro-ducts according to -the invention lies in -the range of 0.9 to 1.5 Cat2/nO . A1203 . 1.3 to 4 SiO2, where the water con-tent is no-t taken into account. The surfactant content of the products dried in the above-described manner lies between 0.01% to 35%, preferably 0.1% to 20% by weight so far as anionic or cationic surface-active compounds are concerned.
Amounts of 0.01% to 0.1% by ~eight of zwitterionic surface-active compounds ~ere found when the above-described method of determination was used.
One can vary the process described in the Examples by pouring both solu~ons simultaneously into the reaction vessel, In the presence of surfactants resistant to hard-ness, the crystallizability of the sodium aluminum silica-tes is less than that of the sodium aluminosilicates prepared in the usual manner, i.e.,in the absence of surfactants.
Therefore, the products prepared according to the directions given in the Examples remain longer or permanently in an x-ray amorphous state.
105038~
The preceding spsci~ic embodiments are illustrative o~ the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art, or disclosed herein3 may be employed without departing from the spirit of the in~ention and the scope o~ the appended claimæ.
~ 41 -~ 1~72~ 77~ 848 - NI~Jr/gk en~rli~3r-~ DISC~S~
In the principal disclosure aluminosilicates are prepared in the presence of ionic surfactants resistant to the - action ~f water hardness ~ormers such as anionic~ cationic, or zwi~terionie water-soluble organic sur~ace-active compounds.
Pre~erably, however, the cationic surface-active compounds are employed in the production o~ the aluminosilicates o~ the invention When the cationic surfactants are employed, . . .
it is believed they occupy sites within the structural framework o~ the aluminosilicates and supply a controlled release o~ cati-onic sur~actant into the wash solution with improved wash results.
-~2-~ ' ~ ~ .
~3t5~L
EX~LES OF WASHING PERFORMANCE
The following alumlnosilicates were used:
A) An amorphous aluminosilica-te according to the invention (This aluminosilicate contains 2.9% by weight of cationic surfactant within its structural framework.) B) A conventional amorphous aluminosilicate. (This alu~-inosilicate contai~s 3.1% b~ weight of cationic sur-factant adsorbed onto its surface.) Preparation of the aluminosilicates ~ and B:
.
A) 12 gm of hexadecyl-trimethylammonium chloride (25% by weight aqueous solu.ion) were diluted with 633 gm of deionizea water. Then, 148 gm of sodium silicate solution (35% by weight, molar ratio SiO2/~a2O - 3.4} were added while stirring. Following ~his addition, a freshly prepared solu-tion of 54.8 gm o~ sodium aluminate (Na2O/~12O3 = 1.2~
dissolved in 160 ~m of deionized wa-ter was added while con-- tinuing stirring. A suspension of the amorphous surfactan~- ~
modified sodium aluminosilicate was formed.
After -three hours of continued s-tirring, the pre-cipitate was separated by suction fil-tration, washed four times with 50 ml of deionized wa-ter and dried at 70~C for 24 hours. The dried product had the following composition-0.95 Na2O A123 2.4 SiO2 4.4 H2O
!
Surfactant conten-t - 2.9% by weight. - ~
-~3-B
lq~S~31~
B~ 148 gm of sodium silicate solution (same as under A) ¦ were diluted wi~h 637 gm of deionized water. Then while - stirringl 54.8 gm of sodium aluminate (same as under A) dis-solved in 160 gm of deionized wa-ter were added. Tne fo~med S suspension of the amorphous sodium aluminosilicate was stirred ~or three hours. Then, the precipitate was separated by suction fi~-tration, washed four times with 50 ml o deionized water and dried at 70C -Eor 24 hours.
100 gm of the dried amorphous sodium aluminosilicate were suspended in a solution of 20 gm of hexadecyl trimethyl-am~onium chloride (25% by weight aqueous.solution) in 180 gm of deionized water. After stirring for three hours, the solids were separated by suction filtration and dried fox 24 hours at 70C.
The dried product had the following composition:
_ 0.95 Na~O ~12O3 2.5 SiO2 4.5 H2O
Surfactant content = 3.1% by weight.
(The difference of the surfactant content of 0.2%
b~ weight between products A and B was believed to be immaterial.) The washing performance of products ~ and B, respectively, was tested in the following manner:
The sodium aluminosilicate was added to the wash liquor at a dosage level of 2.4 gm of active substance per liter in the presence of 7 ~m per liter of the ~ollowing j liquid laundry de-tergen-t formulations:
~3 .. . .. . . ...
~05~384 Formulation ~
Percent by Weiyht ¦ Alkyl benzene sulfonate, sodium salt 6.4 The condensation product of a hydro-genated tallow alcohol with 5 mols of ethylene oxide per mol of alcohol 2~2 Soap 3~
Sodium silicate 3.0 Sodium perborate 26.5 - .
Magnesium silicate ~.0 Sodium tripolyphosphate 3.0 Sodium citrate 3.0 Sodium sulfate 4.0 EDTA 0.2 Residue water up to 100 Formulation II
. Same as Formulation I, but the alkyl benæene sulfonate was replaced b~ the condensation product o~ a hydrogenated tallow alcohol with 14 mols of ethylene oxide pex mol of the alcohol.
The tests were carried out in the L~underometer at a ratio of water/textile equal to 12:1, using water of 16d hardness at 60C and a duration of 15 minutes. ~11 tests were carried out with both formulations using standard-ized soiled textiles (unfinished cotton, resin finishedcotton, pol~esterJcotton).
The experimental results are summarized in Table 1.
-45- ~
E~ ' .
~5~384 T A B L E
! Remiss;on Data Obtained , _ I , Product Unfinished Resin Fin- Polyester. Cotton ished Co-tton Cot-ton _ _ _ I II I II I II
A Invention 60 62 68 76 53 59 B Non-inven- .
tion 54 64 63.5 72 49 57 The results obtained clearly show the superioxity of the product according to the invention. These results show a bet-ter washing performance of the products according to the invention as com~ared wi ~ dried aluminosilicates post---treated wi~h an aqueous solution of surfactant having the.
same or evën a slightly higher amount of surfactant adsorbed onto the surface of the aluminosilicate particles. : -E ~ ~LE TO RELEASE OF SURF~CTA~T
Products C and D were employed, which were prepared similarly as Products A and B of the previous example.
- ~C) An amorphous aluminosilicate according -to -the invention containing 4.7% by weight of cationic surfactant ~i-thin i-ts structural framework ~D) A conventional amorphous aluminosilicate containing 2.8% by weight of cationic surfactant adsor~ed onto its surface.
-46- ' .. ~.... .. .. .. . . . .... " .. .. .. .... ... . . . .
Two-gram samples of the products wer~ treated at room ~emperature with 100 ml of the following liquids for periods of one hour:
a) distilled wa-ter b) water of 16d (German hardness degrees) c) water of 16d, additionally containing 0.1 mol o Na2SO4 per liter.
After treatmentr the mother liquor was separated by suction filtra-tion and the cationic surEactant content of the mother liquor was determined by reverse Epton-titra-~ - tion. Table 2 shows -the cationic surfactant contents observed in the various experiments.
T ~ B L E 2 - 'i .. . -- Reverse Ep-ton-Titration ~g Cationic Surfactant .
a) Distilled water C 5.1 (invention) -- ~ 6.4 (non-invention) b) 16d water C 6.4 (invention) D 5,1 (non-invention~
c) 16d water ~
0.1 mol/l Na2SO4 C 3.8 (invention) D 2.6 (non-invention) i -47- ~r ~' ' ' .
;
~5038~
The results show that increasing the ionic content~
¦ of the trea-tment solution strongly favors the release of the cationic surfactant from the aluminosilicates of the inven-tion relative -to the release of cationic surfactants, wnich 5 have been adsorbed onto previously made and dried alumino-silicates.
The ratio cationic surfactant released by C divided by the cationic surfactant released by D has the following trend:
a) 5,1:6.4 b) 6.4:5~1 c) 3.8:2.6 0.8 1.~5 1~46 We believe that in the case of the aluminosilicates of the invention, the cationic surfactants occupy si-tes within the structural frame, which can also be occupied by sodium ions. Therefore, there will be a competition between .
cationic.surfactants and sodium ions for these sites. A
reoccupation of these sites by the surfactant is less li~ely i~ competing sodium ions are around. Therefore, a relative - increase in the ra-te of surfactant release is observed in the case of aluminosilicates of the invention in the presence of sodium ions.
B
Claims (16)
1. Cation-exchanging, water-insoluble amorphous alumino-silicates containing at least 3 mols of bound water for every mol of Al2O3 and at least 0.01% by weight of a cationic surface-active compound active in the presence of water hardness formers, and having for every mol of Al2O3, from 0.7 to 1.5 mols of Cat2O, where Cat is a cation selected from the group consisting of sodium, potassium and lithium, and from 0.8 to 6 mols of SiO2, said alumi-nosilicates having a calcium sequestering power of from 50 to 200 mg CaO/gm of anhydrous active substance and a particle size of less than 30 µ, and being produced by the precipitation of said aluminosilicate in an aqueous solution, wherein said reaction is conducted in the presence of an aqueous solution of said cationic surface-active compound.
2. The aluminosilicate of claim 1 wherein Cat is a sodium cation.
3. The aluminosilicates of claim 1 containing from 3 to 10 mols of bound water per mol of Al2O3.
4. The aluminosilicates of claim 1 containing from 0.9 to 1.5 mols of Cat2O.
5. The aluminosilicates of claim 1 containing 1.3 to 4.0 mols of SiO2.
6. The aluminosilicates of claim 1 containing 0.01% to 50% by weight, based on the total weight, of cationic surface-active compound.
7. The aluminosilicates of claim 1 containing 0.1% to 35% by weight, based on the total weight, of cationic surface-active compound.
8. The aluminosilicates of claim 1 having a particle size of less than 8 ?.
9. The aluminosilicates of claim 1 wherein said cationic surface-active compound is present in an amount of 0.1% to 20%
by weight.
by weight.
10. The aluminosilicates of claim 1 having a calcium sequestering power of from 80 to 160 mg of CaO per gram of anhydrous active substance.
11. Aqueous suspensions of th aluminosilicates of claim 1 containing from 2% to 50% by weight of said aluminosilicates, said weight based on a product having been dried at 80°C for at least three hours at a pressure of 100 mm of Hg.
12. Suspensions according to claim 11, characterized in that the aqueous phase essentially dissolves and contains only said surfactants active in the presence of water hardness formers.
13. The process for the preparation of amorphous alumino-silicates by reacting water-soluble aluminates with water-soluble silicates in the presence of water and recovering water-insoluble aluminosilicates, the improvement consisting of conducting said reaction in the presence of an aqueous solution of a cationic sur-face compound active in the prsence of water hardness formers.
14. The process of claim 13 wherein said cationic surface-active compounds and said water-soluble silicates are dissolved in said water and said water-soluble aluminates are added thereto.
15. In the process of washing soiled textiles by con-tacting soiled textiles with an aqueous solution containing a water softening agent for a time sufficient to disperse or dissolve the soil from said soiled textiles into said aqueous solution, separating said aqueous solution and recovering said textiles substantially soil-free, the improvement which consists of using at least one cation-exchanging, water-insoluble alumino-silicate of claim 1, as said water softening agent.
Claim Based on Supplemental Disclosure
Claim Based on Supplemental Disclosure
16. The process of claim 15 wherein said aluminosilicate producing precipitation reaction is conducted in the presence of a cationic surface-active compound and said aqueous washing solu-tion contains sodium ions.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT777173A AT330100B (en) | 1973-09-07 | 1973-09-07 | PROCESS FOR THE PRODUCTION OF NEW, RONT-GENERAL AMORPHERIC, CATION-EXCHANGING ALUMINUM SILICATES, WHICH MAY CONTAIN BONDED WATER |
| AT838273A AT330101B (en) | 1973-10-01 | 1973-10-01 | PROCESS FOR THE PRODUCTION OF NEW, RONT-GENERAL AMORPHERIC, CATION-EXCHANGING ALUMINUM SILICATES, WHICH MAY CONTAIN BONDED WATER |
| AT1009873A AT330102B (en) | 1973-12-03 | 1973-12-03 | PROCESS FOR THE PRODUCTION OF NEW, RONT-GENERAL AMORPHERIC, CATION-EXCHANGING ALUMINUM SILICATES, WHICH MAY CONTAIN BONDED WATER |
| US05/811,964 US4126574A (en) | 1973-09-07 | 1977-06-30 | Surfactant-containing aluminosilicates and process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050384A true CA1050384A (en) | 1979-03-13 |
Family
ID=27422232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA208,785A Expired CA1050384A (en) | 1973-09-07 | 1974-09-09 | Surfactant-containing aluminosilicates and process |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1050384A (en) |
-
1974
- 1974-09-09 CA CA208,785A patent/CA1050384A/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4126574A (en) | Surfactant-containing aluminosilicates and process | |
| CA1062984A (en) | Stable aqueous suspension of water-insoluble, calcium-binding aluminosilicates and organic suspending agents | |
| CA1254581A (en) | Peracid and bleach activator compounds and use thereof in cleaning compositions | |
| DE69516182T2 (en) | AMINONITRILE INTERMEDIATE PRODUCTS FOR THE PRODUCTION OF ALAMINE DIETACRIC ACID | |
| CA1230206A (en) | Softener-containing washing agent | |
| CA1178383A (en) | Sequestering of ca su xx and me su xx in aqueous media using zeolite mixtures | |
| CA1117733A (en) | Preparation of finely-divided, water-insoluble silicate cation-exchangers with a narrow particle size spectra | |
| DE68901737T2 (en) | ALKYLSULPHONYLPERCARBONIC ACIDS AND THE BLASTING AND CLEANING COMPOSITIONS CONTAINING THEM. | |
| US4201689A (en) | Process for the production of tenside-containing cation exchanger aluminosilicates | |
| CA1251440A (en) | Adsorbents based on phyllosilicic acids which have been modified so as to be organophilic | |
| EP0087035B1 (en) | Zeolite-containing detergent compositions and process for preparing same | |
| CH630322A5 (en) | STABLE SUSPENSIONS OF WATER-INSOLUBLE SILICATES CAPABLE OF BONDING CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS. | |
| US2174506A (en) | Process of reacting alicyclic hydrocarbons with chlorine and sulphur dioxide and products thereof | |
| CA1050384A (en) | Surfactant-containing aluminosilicates and process | |
| JPH1171108A (en) | Synthetic magnesium silicate | |
| DE68928767T3 (en) | Imido-percarboxylic acids | |
| EP0015366A2 (en) | Process for the preparation of aqueous solutions of alkali-organosiliconates | |
| JPS5833917B2 (en) | How to wash and bleach textiles | |
| DE69616085T2 (en) | AMINONITRILE INTERMEDIATE PRODUCTS FOR THE PRODUCTION OF 2-HYDROXYETHYLIMINODIACETIC ACID | |
| FI66130C (en) | SYNTHETIC FINISHED CRYSTALS SILICONE ALUMINUM FOUNDARY FOAR DESS FRAMSTAELLNING SAMT DESS ANVAENDNING | |
| JPH0249299B2 (en) | ||
| AT375391B (en) | METHOD FOR WASHING OR BLEACHING TEXTILES AND MEANS THEREOF | |
| DE2330436A1 (en) | USE OF SUBSTANCE MIXTURES, BASICALLY CONTAINING CARBOXYMETHYL POLYGLYCOL ETHER, AS SCALING INHIBITOR IN LAUNDRY AND CLEANING AGENTS | |
| SU983045A1 (en) | Method of filtering silica containing suspensions | |
| CH624914A5 (en) | Process for preparing cation-exchanging alkali metal alumosilicates |