CA1142338A - Mixture of amines and polyether compounds its production and its use as a heat stabiliser - Google Patents
Mixture of amines and polyether compounds its production and its use as a heat stabiliserInfo
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- CA1142338A CA1142338A CA000345458A CA345458A CA1142338A CA 1142338 A CA1142338 A CA 1142338A CA 000345458 A CA000345458 A CA 000345458A CA 345458 A CA345458 A CA 345458A CA 1142338 A CA1142338 A CA 1142338A
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- polyether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
- C08C1/145—Heat-sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Colloid Chemistry (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
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Abstract
ABSTRACT OF THE DISCLOSURE
A mixture comprising from 2 to 30 parts by weight of ammonia and/or monoamlne and/or polyamine and from 70 to 98 parts by weight of aminopolyether and/or polyether-based non-ionic surfactants, a process producing said mixture by mixing the components in any order at temperatures in the range of from 0 to 50°C, and its use as heat sensitizer in a process for heat-sensitising a natural and/or syn-thetic latex in which the latex is adjusted to a pH-value below 7.
A mixture comprising from 2 to 30 parts by weight of ammonia and/or monoamlne and/or polyamine and from 70 to 98 parts by weight of aminopolyether and/or polyether-based non-ionic surfactants, a process producing said mixture by mixing the components in any order at temperatures in the range of from 0 to 50°C, and its use as heat sensitizer in a process for heat-sensitising a natural and/or syn-thetic latex in which the latex is adjusted to a pH-value below 7.
Description
33~3 The present invention relates to a mixture of ammonia and/or monoamines and/or polyamides an~ polyether based compounds, to its production by a standard mixing process and to its use as a heat sensitiser in the production of heat-sensitive natural and/or synthetic latices.
German Auslegeschrift No. 2,226,269 describes a number of heat sensitisers, such as for example polyvinyl alkyl ethers, water-soluble polyacetals, alkoxylated polysiloxanes and cation-active substances, and also their disadvantages. That Auslegeschrift and also German Auslegeschrift No. 2,263,921 describe a process for the heat sensitisation of polymer disperions in which alkoxylated amines having inverse solubility in water are added to the polymer dispersions and the pH of the mixture is subse~uently adjusted to a value below 6.
However, this particulax process is also unsatisactory, particularly because o~ the fact that the quantities of inversely soluble alkoxylated amines required, based on the amount of polymer, are very high. Alkoxylated alkyl amines containing from 10 to 24 carbon atoms in the alkyl radical are described as heat sensitisers in Swiss Patent Application No. 4600/73, published January 31, 1975. ~owever, these alkoxylated alkyl amines again have to be used in large ~uantities for heat sensitisation.
The object of the present invention is to provide a heat sensitiser which does not have any of the disadvantages referred to above.
Accordingly, the present invention provides a mixture comprising from 2 to 30 parts by weight o at least one member selected from the group consisting of ammonia, monoamines other ;
~Z33~3 than aminopolyethers and polyamines other than polyaminopolyethers and from 70 to 98 parts by weight of at least one member selected from the group consisting o~ aminopolyether based non-ionic sur~actants and polyether-based non-ionic surfactants.
The present invention also provides a process for producing the mixture of the present invention which is characterised in that ~rom 2 to 30 par-ts by weight of at least one member selected from the group consisting o-f ammon.ia, monoamines other than aminopolyethers and polyamines other than polyaminopolyethers are mixed in known manner with from 70 to 98 parts by weight of at least one member selected from the group consistin~ of aminopolyether based non-ionic surEactants and polyethex-based non-ionic surfactants in any order at temperatures in the range ~rom 0 to 50C and preferably at -temperatures in the range from 10 to 35C.
The present invention also pro~ides the use of the mixture of the present invention as a heat sensitiser in a process for the heat sensitisation of a natural and/or synthetic latex in which the latex mixture is adjusted to a pH-value below 7.
l`he aminopolyethers which may be used in accorda~ce with the present invention are obtained by polyalkoxylating aliphatic or aromatic monoamines or polyamines.
The compounds used as aliphatic or aromatic monoamines or polyamines Eor the alkoxylation reaction may be, Eor example, methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, allyl, oleyl, hydroxy ethyl, hydroxy propyl, cyclohexyl, dimethyl, diethyl, dipropyl, dibutyl, benzyl, phenyl, ethylene di-, diethylene tri-, triethylene tetra-, tetraethylene 233~
penta-, pentaethylene hexa-, propylene di-~ butylene di-, hexamethyl di- or isophorone diamine.
For producing the amino poly ethers, the amines are alkoxylated by known processes. The alkylene oxides used are, preferablyl ethylene and propylene oxide. It is possible to produce pure amino polyethylene oxides and polypropylene oxides.
However, products containing ethylene and propylene oxide in copolymerised or block-copolymerised form may also be used. The amino polyethers preferably contain from 3 to 50 ethylene oxide units and/or from 3 to 40 propylene oxide units.
It is of advantage to use those amino polyethers which can be dissolved or emulsified in water. The -2a-~,'
German Auslegeschrift No. 2,226,269 describes a number of heat sensitisers, such as for example polyvinyl alkyl ethers, water-soluble polyacetals, alkoxylated polysiloxanes and cation-active substances, and also their disadvantages. That Auslegeschrift and also German Auslegeschrift No. 2,263,921 describe a process for the heat sensitisation of polymer disperions in which alkoxylated amines having inverse solubility in water are added to the polymer dispersions and the pH of the mixture is subse~uently adjusted to a value below 6.
However, this particulax process is also unsatisactory, particularly because o~ the fact that the quantities of inversely soluble alkoxylated amines required, based on the amount of polymer, are very high. Alkoxylated alkyl amines containing from 10 to 24 carbon atoms in the alkyl radical are described as heat sensitisers in Swiss Patent Application No. 4600/73, published January 31, 1975. ~owever, these alkoxylated alkyl amines again have to be used in large ~uantities for heat sensitisation.
The object of the present invention is to provide a heat sensitiser which does not have any of the disadvantages referred to above.
Accordingly, the present invention provides a mixture comprising from 2 to 30 parts by weight o at least one member selected from the group consisting of ammonia, monoamines other ;
~Z33~3 than aminopolyethers and polyamines other than polyaminopolyethers and from 70 to 98 parts by weight of at least one member selected from the group consisting o~ aminopolyether based non-ionic sur~actants and polyether-based non-ionic surfactants.
The present invention also provides a process for producing the mixture of the present invention which is characterised in that ~rom 2 to 30 par-ts by weight of at least one member selected from the group consisting o-f ammon.ia, monoamines other than aminopolyethers and polyamines other than polyaminopolyethers are mixed in known manner with from 70 to 98 parts by weight of at least one member selected from the group consistin~ of aminopolyether based non-ionic surEactants and polyethex-based non-ionic surfactants in any order at temperatures in the range ~rom 0 to 50C and preferably at -temperatures in the range from 10 to 35C.
The present invention also pro~ides the use of the mixture of the present invention as a heat sensitiser in a process for the heat sensitisation of a natural and/or synthetic latex in which the latex mixture is adjusted to a pH-value below 7.
l`he aminopolyethers which may be used in accorda~ce with the present invention are obtained by polyalkoxylating aliphatic or aromatic monoamines or polyamines.
The compounds used as aliphatic or aromatic monoamines or polyamines Eor the alkoxylation reaction may be, Eor example, methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, allyl, oleyl, hydroxy ethyl, hydroxy propyl, cyclohexyl, dimethyl, diethyl, dipropyl, dibutyl, benzyl, phenyl, ethylene di-, diethylene tri-, triethylene tetra-, tetraethylene 233~
penta-, pentaethylene hexa-, propylene di-~ butylene di-, hexamethyl di- or isophorone diamine.
For producing the amino poly ethers, the amines are alkoxylated by known processes. The alkylene oxides used are, preferablyl ethylene and propylene oxide. It is possible to produce pure amino polyethylene oxides and polypropylene oxides.
However, products containing ethylene and propylene oxide in copolymerised or block-copolymerised form may also be used. The amino polyethers preferably contain from 3 to 50 ethylene oxide units and/or from 3 to 40 propylene oxide units.
It is of advantage to use those amino polyethers which can be dissolved or emulsified in water. The -2a-~,'
2~
water-soluble amillo polyethers ~lay even bc products having inverse solubility.
However, basically i.nsoluble amino polyethers, for e~ample those with relatively high propylene o~icle contents, may also be used in e~ulsified form. For emulsification, emulsifiers such as, for example, alkyl sulphonates, alkyl aryl sulphonates, fatty alcohol sulphates or -fatty acid salts may be added to the usual polye~her ~nes m ouantities of for ex~mple frGm 0.5 to 10% by weight 1~ based on the weight of insoluble polyether ~nes.
Where the insoluble polyether amines are used in combination with the non-ionic surfactants for heat sensitisation, there is generally no need for other emulsifiers to be added.
Examples o~ the amino polyethers for use according to the invention are those such as ethQ~ylates of ethanol~ne, benzyl amine, cyclohexyl amine, clodecyl amine, oleyl amine, ethylene diamine ancl hexamethylene diamine containing from 4 tc~40 moles of ethylene oxide units, prop~lates of methyl amine, isopropanol.aLuine~ e-thylene cliamine and hexamet~lylene diamine containing from 4 to 40 moles of propylene o~ide, units, alkoxylates o~ m2thyl ~ne, cyclohexyl amine, isopropanolamine, e-thanolamine, ethylene diamine, hexamethylene diamine, dodec~l amine and oleyl amine con-taining from 4 to 30 moles each of ethylene and propylene oxi.de units.
Suitable polyether-based non-ionic surfactants are any surface active polyalko.~yaltes of alcohols, aliphatic carboxylic acicls, aliphatic carbo~ylic amicles and alkyl sulpollic acid amides preferably containing fro~
10 to ~0 c~rborl atom~, ancl o~ all;ylated phenols, ap~-thols ar~cl hydroYy cliphenyls preferably colltain:Ln-r ~rom 6 to 16 carbon ~toms in -the alkyl racli.cal) the polyalkoYyl racli.cals being derived from alkylene o~.ide
water-soluble amillo polyethers ~lay even bc products having inverse solubility.
However, basically i.nsoluble amino polyethers, for e~ample those with relatively high propylene o~icle contents, may also be used in e~ulsified form. For emulsification, emulsifiers such as, for example, alkyl sulphonates, alkyl aryl sulphonates, fatty alcohol sulphates or -fatty acid salts may be added to the usual polye~her ~nes m ouantities of for ex~mple frGm 0.5 to 10% by weight 1~ based on the weight of insoluble polyether ~nes.
Where the insoluble polyether amines are used in combination with the non-ionic surfactants for heat sensitisation, there is generally no need for other emulsifiers to be added.
Examples o~ the amino polyethers for use according to the invention are those such as ethQ~ylates of ethanol~ne, benzyl amine, cyclohexyl amine, clodecyl amine, oleyl amine, ethylene diamine ancl hexamethylene diamine containing from 4 tc~40 moles of ethylene oxide units, prop~lates of methyl amine, isopropanol.aLuine~ e-thylene cliamine and hexamet~lylene diamine containing from 4 to 40 moles of propylene o~ide, units, alkoxylates o~ m2thyl ~ne, cyclohexyl amine, isopropanolamine, e-thanolamine, ethylene diamine, hexamethylene diamine, dodec~l amine and oleyl amine con-taining from 4 to 30 moles each of ethylene and propylene oxi.de units.
Suitable polyether-based non-ionic surfactants are any surface active polyalko.~yaltes of alcohols, aliphatic carboxylic acicls, aliphatic carbo~ylic amicles and alkyl sulpollic acid amides preferably containing fro~
10 to ~0 c~rborl atom~, ancl o~ all;ylated phenols, ap~-thols ar~cl hydroYy cliphenyls preferably colltain:Ln-r ~rom 6 to 16 carbon ~toms in -the alkyl racli.cal) the polyalkoYyl racli.cals being derived from alkylene o~.ide
3~ preferably from ethylene arlcl/or propylerle o~ide. Fro~l 3 -to 50 e~ ylerle o~ide ancl/or from ~ -to ~0 propylene o~ide 3~
units are generally present~
The compourlds of the above type, their proclltc-tion and their physical properties are described in detail in numerous publications, for example in K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, Wiss.-Verlags GmbH, Stuttgart 1964, on pages 864 et ~g. lt is pre-ferred to use -those products which can be either dissolved or emulsi~ied in ~ater. Examples of products such as these are fatty alcohol, fat-ty acicl and fatty acid amide ethocylates preferably those containing from 7 to 50 ethylene o~icleunits, octyl and nonyl phenol ethoxylates preferably those containing from 7 to 50 ethylene o~ide units and benzyl hydroxy diphenyl etho~ylates preferably those containing lrom 7 to 30 ethylene oxide units.
Other polye-ther-basi3cl non-ionic surfactants which may be used in accordarlce with the presen-t invention are ,~ a~ylene Yide ~lock polymers o-~ the type known as k~c~r~. The production, structure and properties of th~se products, which are formed by the actionc~ ethylene oxide on insoluble polyalkylene oxicles, preferably polypropylene o~ides, are described for e~ample in the aforementioned p-ublication by K. Lindner on pages 1052 et secl.
It is preferred -to use only aminopolyetheI~s as the mi~ng co~ponent.
In the process according to the present in~ention, ammonia, monoamines or- polyamines act as coagulation reagents in the acid pH-range. Preferred monoamines or polyamines are water-soluble amines such as, for example, methyl amine, dimethy] amine, trimethyl amine, ethyl aluine~ diethyl amine, propyl amine, isopropyl alui~e, buty~ aluine, isobutyl alL~i~le~ cyclohe~yl amine, ethylene di~loine, cliethylene tria~ine, triethylene tetramine, tetI~aetllylene pental~ine, penlcLethyleIle he~amirle, ~ ~ ~ ~ ~ ~r~
;3'3 propyl~ne diamine, butylene diamine and he~amethylene diamine.
So far as the activity o~ the amines is concerned, it has been found that polyamines are ~eneral].y more ac-tive than ammonia.and the monoamines, i.e they may be used in smaller quantities.
For producing the heat-sensitisable synthetic polymer latices, standard ole~inically unsaturatecl monomers may be polymerised in aqueous emulsion. Examples o~
the production of lactices such a~ these may be found in German Pa-tent No. 1,243,394 and in German O~fenlegungsschrifts Nos. 2,232~526 and 2jO05J974.
Suitable monomers are any radically polymerisable ole-finically unsaturated compounds, such as for examp].e ethylene, butadiene, isoprene, acrylonitrile, styrene, divinyl benzene, a-methyl styrene, methacrylonitrile, acrylic acid~ methacrylic acicl, 2-chlo.ro-1,3-butadiene, es-ters of acrylic acid and methacrylic acid with Cl Cs alcohols or polyols, acrylarnide, methacrylamide, N-methylol ~meth) acrylamicle, (meth)acYyla~ido-N-methylol methyl ether, itaconic acid, maleic acid, ~umaric acid, diesters and semiesters o~ unsaturated dicarbo~ylic acids, vinyl chloride, vinyl acetate, vinylidine chloYide or combinations thereof.
2~ The polymerisation reaction is carried out in the presence of emulsifiers, for which purpose the usllal non-ionic or anionic emulsifiers may be used either inelividually or in combination with one another. The total g~lantity of emulsifier normally amounts to betwQ~n about 0.1 ~nd 10 ~b by ~ieight, basecl on the monomers.
~ he e~lllsion polymerisation reaction may be initiated by radical ~ormers, preferably by organic pero~ e compounds, which ar2 r.or~ used .Ln qu.~nti-ties of frcm 0.01 -to " ~o b~ , ba~(l on -tlle ~ hto~ {lor~ . D~y~lld~
3~ Llpon -the monolllel coulbination llsed, small. quanti-ties o~
reglllators~ ~or example mercaptclns or halogeIlated hydro~
3~3 caxbons, ulay also be used -for reducing the molecular weigh-t of the polymer produced. The emulsion poly-~erisa-tion reaction rnay be carriea out in two ways:
The total quantity o-f monomers and mos-t of the aqueous phase containing the emulsifiers may be initially introd~lcecl into the reaction vessel, the polymerisa~tion reaction intia-ted by adding the initiator and the rest o~ the aqueous phase added either continuously or in batches during the polymerisation reaction. The lQ so-called "~onomer feed" technique may also be used.
In this case 9 only part of the monomers and the aqueous phase containing the emulslfier is initially introduced into the reaction vessel, the rest of the monomers and the aqeous phase being added continuously or in batches cornmensurately with the conversion after the polymerisation reaction has been startecl. The propoYtion o~ monomer added may be pre-emulsified in -the aqueous phase. Both of the above processes are known.
Natural rubber late~ is mentioned as one example of natural polymer la-tices.
Ad~tives may be introduced into the heat-sensitisable latices before they are processed. E~amples of additives are dyes, pigments, fillers, thickeners, anti-agers, ~ater-soluble resins and vulcanisation chemicals.
The latex mixtures are adjusted to pH-values below 7 either wi-th or~anic carboxylic acids such as, -for example, formic acid, acetic acid, succinic acicl maleic acid or m:LYtures thereof preferably in aq!leous solutic~, or else with dilu-te mineral acids ~he coagLIlation reagents, am~onia and/or ~onoamines and/or polyamilles, and -the polyether compoLIIlds may be added in any order to the polymer latices which have a polyu~er conterlt of from 5 to 55 o~b by ~veight and preferably of frol~ 5 to LL5 /0 by ~eigll-t. ~he mi~ture Of COagllla~.,iOn rea~ellts an.l polyether compoLlnds Lnay also be separately prepared by the process accordiIIg to the present invention and then subsequent]y addecl. Based on the poly~er content, the coagula-tion reagents are added in quantities of f`roLn 0.01 to 4 /0 by weight, preferably in quantitites of from 0.05 to 2.5 /0 by weight, whilst the polyether compounds are added in quantities of from 0.5 to 10 ,/c by weight and preferably in quantities of f`rom 1 to 5 ~0 by weight. ~he quantities of coagulation reagent and polyether compounds used are inter-dependent. The larger the quantity of coagulation reagent used, the lower the ooagula-tion point after heat sensitisation by acidification for a constant quantity of polyether, where-as the larger the quantity in which the polyether compound is used, the higher the coagulation point for a constan-t concentration of coagulation reagent.
The mi~ture of polymer latex, coagulation reagent and polyether stabilisers may be stored virtually indef initely and may therefore be heat-sensitised by acidification even a-fter prolonged storage.
During acidification the plI values are acljusted to preferably from 6 to ~ ancl, ~rith particular preference, from 5 to 3, One particular advantage of the systetn lies in the fact that the coagulation point is in the range from pH 6 -to 3 virtually irrespective of the pN
value. It is only at lower pH values that the coagulation point of a mixture falls, whereas the sys-tem cannot generally be heat-sensitised at pH-values above 7.
In some cases, the mechanical s-tability of the m~xtures may be further increased by the addition o-f` fro~
0.5 to 3 /0 by weight, based on the ~eight of polymer, of anion-~ctive emulsifiers, preferably those such as alkyl sulphona-tes or alkyl aryl sulphonates.
~ i~tures of latices and coagl~lation lea~ents cannot be lleat-~sellsitisecl ~ri-thollt polyetller col~pourLcls. In tllis ca.se, 130i(ii.~ 1t;i.OlL iS l,(:~COLilparlieCl by either speckle ~5 formation illLmeclicltely or after standin~, or else by co~plete coa~ula-tion of the ~i~-tuIe a-t temperatures as low as roo~ tempera-ture. ~he ~lon-ionic surfactants and a~inopolyethers suitable for use as -the polyether compounds ~lay be employed either individually or in cor~bination with one another.
Sorne of the polyether amines are described as heat sensitisers in the aforernentioned German Auslegeschrifts Nos, 2,226,269 and 2,263921 and in Swiss PateIl-t Application ~'o 4600/73, These in~ersely soluble aminopol~etllel-s are ef`~ective as stabilisexs in the process accordin~ to the present in~ention in such small quantities that 7 ~ithou-t the addition of ar~monia or amine as coagulation reagent, no heat sensitation of the mi~ture occurs after aoidification.
_ A solution of ~ g of ethylene diamine and ~ g o~ an ethoxylated nonyl phenol ~10 moles of ethylene oxide ~its mole) in 190 g of water is added to 300 parts by ~eight ot` a 43.5 ~ late~ of a copolymer o~ 46 o,b by weight of / styrene, 50 /0 by weight of butadiene, 2 ~/O by weight of acrylic acia and 2 /0 by weight o-f N-methylol acryl-aruide. A storable mi~ture is obtained, The mi~ture thus r~btained is adjusted to pH 3 with 10~ by weight aqueous maleic acid and its coagulation point determined by the following method:
Approximately 10 g of the heat-sensi-tised mi~-ture is weighed into a glass beaker which is then placed in a water bath having a constant temperatuxe of S0C.
while the mi~ture is unlformly stixred using a thermometer, its coagulation ~ehaviour and the increase in teulperature ~hich it undergoes are followecl, The coagulativn point of the mi~ture is defined a.s the teDlperat-ure at ~hich the polymer an~ the aqueous phas~
are colupletely anrl de~initively separater~.
A coa~-llation pOi~lt of ~3;'C is deter~linecl. I- no nonyl phenol etho~xylate is arlded~ the mi~ture iD~nediately coagulates on addi-tion O:r the maleic acid.
3~3 g If no ethylene dia~ine is addecl, the mixture is no-t heat-sensiti~e after acidification, EXAl~PLE ~
The procedure is that set out in Example l, except that a solution of 1~2 g of ethylene diamine and 6 g of`
the nonyl phenol ethoxylate in 192,8 g of water is used, The mi~ture is acidified with maleic acid. The following coagulation points are determined in dependence upon the adjusted pH-value.
lO pH-~alue 8 7 6 5 4 3 2 Coagulation point C (x) 72 49 42 41 41 3 (x) _ no coagulation E ~MPLE
Following the procedures of Example l, a solution of 2 g of ethylene dia~line and 5 g of nonyl phenol ethocylate (20 r,oles of ethylene oxide~its per mole) m 193 g of water is added to the la-te~, Coagulation poin-t at pE 3: 4~C.
EXA~PLE 4 Following the procedures of Example l, a solution o-f 1,9 g of cyclohe~yl amine and 6 g of an ethoxylated benzyl hydroxy diphenyl (11 moles of ethyléne c~ide units per mole) in 192.1 g of water is added to the late~.
Coagulation point at pH 3: 40C.
EXA~LE 5 Following the procedures of Example 1, a solution of 0.5 g of cyclohexyl amine and 2 g of an ethoxylatecl nonyl p'nenol (10 moles of et'nylene r~ide units per mole) in 197.5 g o~ water is added to the latex. Coagulation 30 point at pH 5: 44C. Coagulation point at pH 3: 43C.
E~LPLE 6 .__ A solution of 0.4 g of ethylene diallline alld 5 g of an isopropanolamine alko~laterl ~tth 6 moles of propylene ~ide1mi'~s per r~o~e hl 194.~ g of ~ate~ is adde~ to 'he lat~
3> follo~in~ the procedures of E~Yaluple 1~ Coaglllation point a-t pH ~: 44''C.
2~8 If, in a comparison testj no ethylene diamine is added, the mixture is not heat-sensitive after acid-ification. If, by contrast, th0 propoYylated amine is not adcled, the miæture immediately coagulates on addition of the maleic acid.
EXA~
Following the procedures of Example 1, a solution of 0.4 g of ethylene diamine and 6 g of an ethylene diamine ethoxylated with 20 moles of e-thylene oxide units per mole in 193.6 g of water is added to the latex.
Coagulation point at pH 3: 48C.
If~ in a comparison tcst, I10 ethylene diamine is added, the mixture is not heat-sensitive after acidification.
EX~IPLF 8 Following the procedures of E~ample 1, a solu-tion of o.6 g of ethylene cliamine, 6 g of an ethanolamine ethc~ylated with 5 moles of ethylene oxide units per mole and 2 g of a nonyl phenol ethoxyla-ted (10 moles of ethylene c~ide units per mole) in 191~4 g of water is added to the ~atex. Coagulation point at pH 3 51C.
If, in a comparison test, no e-thylene diamine is added, the mixture is not heat-se~sit:ive after acidification~
EXA~PLE g Following the procedures of Example 1, a mi~ture of 0,4 g of ethylene diamine, 4 ~ of an isopropanolamine alkoxylated with 25 moles of propylene oxicle units per mole, 2 g of a nonyl phenol e-thoxylated with 10 moles of 3~ ethylene oxide units per mole a~d 10 ~ of a 10% aqueous sodiulll alkyl aryl sulphonate solu-tion in l~.6 g of ~ater is a~ded to -the late~. Coagulat:iorl ~)o:int at pH 3: 44C.
I~, in a col~lparisorl test, no ethylene diallllne is added, tile miYt~l-re ls not heat-sensitive after acicl--~5 ification.
23~
E~SPLE 10 Following the proceclllres of E~ample 1, a mixture of 3 g of a 25% by weight aqueous am~onia solution, 4 g of an isopropanol-amine alkoxylated wi-th 25 moles of propylene oxide per mole, 2 g of a nonyl phenol etllo~xyla-ted with 10 moles of ethy-lene o~ide units and 10 g of a 10~ byr~eight aqueous sodium alkyl sulphonate solution in 1~1 g of water is addecl to the latex.
The mixture is acidified with 20~ by weight of maleic acid solution.
pH-values ~ 8 7 6 5 4 3 2 Coagulation point (C) (~) (x) 61 43 41 40 40 38 (x) no coagulation If no ammonia is aclded, the mixtu:re is not heat-sensitive after acidi:fica-tion.
Followin~ the procedures of Example 1, a mi~ture of 3.0 g of 25% by weight aqueous ammonia, 4 g of an isopropanolamine alko~ylatecl with 19 moles of propylene oxide unit per mole and 10 g of a 10% aque~ls sodi~ alkyl aryl sulp~lonate solution in 183 g of water is aclded -to the latex. The mi~YtUre is acidified with 20 % -by ~7eight aqueous maleic acid.
pH-value 8 7 6 5 4 3 2 Coagulation point (C) (~) (x) 44 43 42 42 40 (x) no coagulation Without the adclition of amrnonia, the mi~ture is not heat-sensitive after aciclification.
E~MPLE 12 Following the proceclures of E~ample 1, a mix-tllre or 2.6 g of 25% by weight of a~leous ammonia and 3 g of an isopropanol-3o a~ine alkoxylated with 10 ~oles of propylene oxlde~its pe7-mole in 19~L.4 ~ of water is added ~o -the la-te~. T}le muxture is acidiiied with 20~ by weight a~leous ~leic acld.
p~l-Y~l~lc~ ~ 7 G 5 'L 3 `' Coa~ulatloll poirlt (C) (x) ~7 1L2 'LO 3~ 3~ 36 (x) no cocaglllat-ion Wit~lout the acldition of aDm~orlia~ the mi~tllre is not 3~3 heat-sensitive after acidi-fication.
E~MPLE l3 Followlng the procedures of Example l, a solu-tion of 2.4 g of 25~ by weight a~leous a~ncnia and 4 g of dodecyl amine co-aIkoxylated with 1Q moles of ethylene oxide ~its ~nd lO ~oles of propylene oxide in 193.6 ~ of water is added to the latex. Coagulation point at pH 3: 38C.
If, in a comparison tes-t, no a~mQnia is added, the mix-ture is not heat-sensitive after acidification.
E~IPLE l~
A solution of 0 8 g of cyclohe~yl amine and 5 g of an oleyl amine ethoxylated with 20 moles of ethylene oxide units per mole in 64.2 g o~ water is added to 250 parts by weight of 40% by w~ight latex of a copolymer of 64 % by weight of butadiene, 31 /0 by weight of acrylonitrile, 3.5 /0 by weight of N-methylol acrylamide and l.5 /0 by weigh-t of acrylamide. A storable mi~ture is obtained.
The mixture thus obtained is adjusted to pH 3 with 10~ by weight ac~lec~s maleic acid, acetic acid or succinic acid and its coagulation point determined. Coagulation point:
44C.
If no e-thoxylated oleyl amine is added, the mixtuIe coagulates immediately aEter acidifica-tion. If, in contrast, no cyclohe~yl a~ine is added, the mixture is no-t heat-sensitive after acidification.
EXAMPLE l5 Following the procedures of Example l4, a ~i~ture of 4 g of a 25~ by weight ac~eous ammonia solution, 3 g of an isopropanolamine propoxyla-ted wi-th 25 moles of propylene oxide units psr mole and 61 g of water is added to the latex.
r~he r~xtu.re is acidi~ied with 20~ ~y weight maleic acid. Co-agula-tion poirlt nt p~I 3: ~5C.
Witholl-t the aclclitioll of nl~noll:ia, -the ~ ture is not hea t-s~llsit:i~e .
units are generally present~
The compourlds of the above type, their proclltc-tion and their physical properties are described in detail in numerous publications, for example in K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, Wiss.-Verlags GmbH, Stuttgart 1964, on pages 864 et ~g. lt is pre-ferred to use -those products which can be either dissolved or emulsi~ied in ~ater. Examples of products such as these are fatty alcohol, fat-ty acicl and fatty acid amide ethocylates preferably those containing from 7 to 50 ethylene o~icleunits, octyl and nonyl phenol ethoxylates preferably those containing from 7 to 50 ethylene o~ide units and benzyl hydroxy diphenyl etho~ylates preferably those containing lrom 7 to 30 ethylene oxide units.
Other polye-ther-basi3cl non-ionic surfactants which may be used in accordarlce with the presen-t invention are ,~ a~ylene Yide ~lock polymers o-~ the type known as k~c~r~. The production, structure and properties of th~se products, which are formed by the actionc~ ethylene oxide on insoluble polyalkylene oxicles, preferably polypropylene o~ides, are described for e~ample in the aforementioned p-ublication by K. Lindner on pages 1052 et secl.
It is preferred -to use only aminopolyetheI~s as the mi~ng co~ponent.
In the process according to the present in~ention, ammonia, monoamines or- polyamines act as coagulation reagents in the acid pH-range. Preferred monoamines or polyamines are water-soluble amines such as, for example, methyl amine, dimethy] amine, trimethyl amine, ethyl aluine~ diethyl amine, propyl amine, isopropyl alui~e, buty~ aluine, isobutyl alL~i~le~ cyclohe~yl amine, ethylene di~loine, cliethylene tria~ine, triethylene tetramine, tetI~aetllylene pental~ine, penlcLethyleIle he~amirle, ~ ~ ~ ~ ~ ~r~
;3'3 propyl~ne diamine, butylene diamine and he~amethylene diamine.
So far as the activity o~ the amines is concerned, it has been found that polyamines are ~eneral].y more ac-tive than ammonia.and the monoamines, i.e they may be used in smaller quantities.
For producing the heat-sensitisable synthetic polymer latices, standard ole~inically unsaturatecl monomers may be polymerised in aqueous emulsion. Examples o~
the production of lactices such a~ these may be found in German Pa-tent No. 1,243,394 and in German O~fenlegungsschrifts Nos. 2,232~526 and 2jO05J974.
Suitable monomers are any radically polymerisable ole-finically unsaturated compounds, such as for examp].e ethylene, butadiene, isoprene, acrylonitrile, styrene, divinyl benzene, a-methyl styrene, methacrylonitrile, acrylic acid~ methacrylic acicl, 2-chlo.ro-1,3-butadiene, es-ters of acrylic acid and methacrylic acid with Cl Cs alcohols or polyols, acrylarnide, methacrylamide, N-methylol ~meth) acrylamicle, (meth)acYyla~ido-N-methylol methyl ether, itaconic acid, maleic acid, ~umaric acid, diesters and semiesters o~ unsaturated dicarbo~ylic acids, vinyl chloride, vinyl acetate, vinylidine chloYide or combinations thereof.
2~ The polymerisation reaction is carried out in the presence of emulsifiers, for which purpose the usllal non-ionic or anionic emulsifiers may be used either inelividually or in combination with one another. The total g~lantity of emulsifier normally amounts to betwQ~n about 0.1 ~nd 10 ~b by ~ieight, basecl on the monomers.
~ he e~lllsion polymerisation reaction may be initiated by radical ~ormers, preferably by organic pero~ e compounds, which ar2 r.or~ used .Ln qu.~nti-ties of frcm 0.01 -to " ~o b~ , ba~(l on -tlle ~ hto~ {lor~ . D~y~lld~
3~ Llpon -the monolllel coulbination llsed, small. quanti-ties o~
reglllators~ ~or example mercaptclns or halogeIlated hydro~
3~3 caxbons, ulay also be used -for reducing the molecular weigh-t of the polymer produced. The emulsion poly-~erisa-tion reaction rnay be carriea out in two ways:
The total quantity o-f monomers and mos-t of the aqueous phase containing the emulsifiers may be initially introd~lcecl into the reaction vessel, the polymerisa~tion reaction intia-ted by adding the initiator and the rest o~ the aqueous phase added either continuously or in batches during the polymerisation reaction. The lQ so-called "~onomer feed" technique may also be used.
In this case 9 only part of the monomers and the aqueous phase containing the emulslfier is initially introduced into the reaction vessel, the rest of the monomers and the aqeous phase being added continuously or in batches cornmensurately with the conversion after the polymerisation reaction has been startecl. The propoYtion o~ monomer added may be pre-emulsified in -the aqueous phase. Both of the above processes are known.
Natural rubber late~ is mentioned as one example of natural polymer la-tices.
Ad~tives may be introduced into the heat-sensitisable latices before they are processed. E~amples of additives are dyes, pigments, fillers, thickeners, anti-agers, ~ater-soluble resins and vulcanisation chemicals.
The latex mixtures are adjusted to pH-values below 7 either wi-th or~anic carboxylic acids such as, -for example, formic acid, acetic acid, succinic acicl maleic acid or m:LYtures thereof preferably in aq!leous solutic~, or else with dilu-te mineral acids ~he coagLIlation reagents, am~onia and/or ~onoamines and/or polyamilles, and -the polyether compoLIIlds may be added in any order to the polymer latices which have a polyu~er conterlt of from 5 to 55 o~b by ~veight and preferably of frol~ 5 to LL5 /0 by ~eigll-t. ~he mi~ture Of COagllla~.,iOn rea~ellts an.l polyether compoLlnds Lnay also be separately prepared by the process accordiIIg to the present invention and then subsequent]y addecl. Based on the poly~er content, the coagula-tion reagents are added in quantities of f`roLn 0.01 to 4 /0 by weight, preferably in quantitites of from 0.05 to 2.5 /0 by weight, whilst the polyether compounds are added in quantities of from 0.5 to 10 ,/c by weight and preferably in quantities of f`rom 1 to 5 ~0 by weight. ~he quantities of coagulation reagent and polyether compounds used are inter-dependent. The larger the quantity of coagulation reagent used, the lower the ooagula-tion point after heat sensitisation by acidification for a constant quantity of polyether, where-as the larger the quantity in which the polyether compound is used, the higher the coagulation point for a constan-t concentration of coagulation reagent.
The mi~ture of polymer latex, coagulation reagent and polyether stabilisers may be stored virtually indef initely and may therefore be heat-sensitised by acidification even a-fter prolonged storage.
During acidification the plI values are acljusted to preferably from 6 to ~ ancl, ~rith particular preference, from 5 to 3, One particular advantage of the systetn lies in the fact that the coagulation point is in the range from pH 6 -to 3 virtually irrespective of the pN
value. It is only at lower pH values that the coagulation point of a mixture falls, whereas the sys-tem cannot generally be heat-sensitised at pH-values above 7.
In some cases, the mechanical s-tability of the m~xtures may be further increased by the addition o-f` fro~
0.5 to 3 /0 by weight, based on the ~eight of polymer, of anion-~ctive emulsifiers, preferably those such as alkyl sulphona-tes or alkyl aryl sulphonates.
~ i~tures of latices and coagl~lation lea~ents cannot be lleat-~sellsitisecl ~ri-thollt polyetller col~pourLcls. In tllis ca.se, 130i(ii.~ 1t;i.OlL iS l,(:~COLilparlieCl by either speckle ~5 formation illLmeclicltely or after standin~, or else by co~plete coa~ula-tion of the ~i~-tuIe a-t temperatures as low as roo~ tempera-ture. ~he ~lon-ionic surfactants and a~inopolyethers suitable for use as -the polyether compounds ~lay be employed either individually or in cor~bination with one another.
Sorne of the polyether amines are described as heat sensitisers in the aforernentioned German Auslegeschrifts Nos, 2,226,269 and 2,263921 and in Swiss PateIl-t Application ~'o 4600/73, These in~ersely soluble aminopol~etllel-s are ef`~ective as stabilisexs in the process accordin~ to the present in~ention in such small quantities that 7 ~ithou-t the addition of ar~monia or amine as coagulation reagent, no heat sensitation of the mi~ture occurs after aoidification.
_ A solution of ~ g of ethylene diamine and ~ g o~ an ethoxylated nonyl phenol ~10 moles of ethylene oxide ~its mole) in 190 g of water is added to 300 parts by ~eight ot` a 43.5 ~ late~ of a copolymer o~ 46 o,b by weight of / styrene, 50 /0 by weight of butadiene, 2 ~/O by weight of acrylic acia and 2 /0 by weight o-f N-methylol acryl-aruide. A storable mi~ture is obtained, The mi~ture thus r~btained is adjusted to pH 3 with 10~ by weight aqueous maleic acid and its coagulation point determined by the following method:
Approximately 10 g of the heat-sensi-tised mi~-ture is weighed into a glass beaker which is then placed in a water bath having a constant temperatuxe of S0C.
while the mi~ture is unlformly stixred using a thermometer, its coagulation ~ehaviour and the increase in teulperature ~hich it undergoes are followecl, The coagulativn point of the mi~ture is defined a.s the teDlperat-ure at ~hich the polymer an~ the aqueous phas~
are colupletely anrl de~initively separater~.
A coa~-llation pOi~lt of ~3;'C is deter~linecl. I- no nonyl phenol etho~xylate is arlded~ the mi~ture iD~nediately coagulates on addi-tion O:r the maleic acid.
3~3 g If no ethylene dia~ine is addecl, the mixture is no-t heat-sensiti~e after acidification, EXAl~PLE ~
The procedure is that set out in Example l, except that a solution of 1~2 g of ethylene diamine and 6 g of`
the nonyl phenol ethoxylate in 192,8 g of water is used, The mi~ture is acidified with maleic acid. The following coagulation points are determined in dependence upon the adjusted pH-value.
lO pH-~alue 8 7 6 5 4 3 2 Coagulation point C (x) 72 49 42 41 41 3 (x) _ no coagulation E ~MPLE
Following the procedures of Example l, a solution of 2 g of ethylene dia~line and 5 g of nonyl phenol ethocylate (20 r,oles of ethylene oxide~its per mole) m 193 g of water is added to the la-te~, Coagulation poin-t at pE 3: 4~C.
EXA~PLE 4 Following the procedures of Example l, a solution o-f 1,9 g of cyclohe~yl amine and 6 g of an ethoxylated benzyl hydroxy diphenyl (11 moles of ethyléne c~ide units per mole) in 192.1 g of water is added to the late~.
Coagulation point at pH 3: 40C.
EXA~LE 5 Following the procedures of Example 1, a solution of 0.5 g of cyclohexyl amine and 2 g of an ethoxylatecl nonyl p'nenol (10 moles of et'nylene r~ide units per mole) in 197.5 g o~ water is added to the latex. Coagulation 30 point at pH 5: 44C. Coagulation point at pH 3: 43C.
E~LPLE 6 .__ A solution of 0.4 g of ethylene diallline alld 5 g of an isopropanolamine alko~laterl ~tth 6 moles of propylene ~ide1mi'~s per r~o~e hl 194.~ g of ~ate~ is adde~ to 'he lat~
3> follo~in~ the procedures of E~Yaluple 1~ Coaglllation point a-t pH ~: 44''C.
2~8 If, in a comparison testj no ethylene diamine is added, the mixture is not heat-sensitive after acid-ification. If, by contrast, th0 propoYylated amine is not adcled, the miæture immediately coagulates on addition of the maleic acid.
EXA~
Following the procedures of Example 1, a solution of 0.4 g of ethylene diamine and 6 g of an ethylene diamine ethoxylated with 20 moles of e-thylene oxide units per mole in 193.6 g of water is added to the latex.
Coagulation point at pH 3: 48C.
If~ in a comparison tcst, I10 ethylene diamine is added, the mixture is not heat-sensitive after acidification.
EX~IPLF 8 Following the procedures of E~ample 1, a solu-tion of o.6 g of ethylene cliamine, 6 g of an ethanolamine ethc~ylated with 5 moles of ethylene oxide units per mole and 2 g of a nonyl phenol ethoxyla-ted (10 moles of ethylene c~ide units per mole) in 191~4 g of water is added to the ~atex. Coagulation point at pH 3 51C.
If, in a comparison test, no e-thylene diamine is added, the mixture is not heat-se~sit:ive after acidification~
EXA~PLE g Following the procedures of Example 1, a mi~ture of 0,4 g of ethylene diamine, 4 ~ of an isopropanolamine alkoxylated with 25 moles of propylene oxicle units per mole, 2 g of a nonyl phenol e-thoxylated with 10 moles of 3~ ethylene oxide units per mole a~d 10 ~ of a 10% aqueous sodiulll alkyl aryl sulphonate solu-tion in l~.6 g of ~ater is a~ded to -the late~. Coagulat:iorl ~)o:int at pH 3: 44C.
I~, in a col~lparisorl test, no ethylene diallllne is added, tile miYt~l-re ls not heat-sensitive after acicl--~5 ification.
23~
E~SPLE 10 Following the proceclllres of E~ample 1, a mixture of 3 g of a 25% by weight aqueous am~onia solution, 4 g of an isopropanol-amine alkoxylated wi-th 25 moles of propylene oxide per mole, 2 g of a nonyl phenol etllo~xyla-ted with 10 moles of ethy-lene o~ide units and 10 g of a 10~ byr~eight aqueous sodium alkyl sulphonate solution in 1~1 g of water is addecl to the latex.
The mixture is acidified with 20~ by weight of maleic acid solution.
pH-values ~ 8 7 6 5 4 3 2 Coagulation point (C) (~) (x) 61 43 41 40 40 38 (x) no coagulation If no ammonia is aclded, the mixtu:re is not heat-sensitive after acidi:fica-tion.
Followin~ the procedures of Example 1, a mi~ture of 3.0 g of 25% by weight aqueous ammonia, 4 g of an isopropanolamine alko~ylatecl with 19 moles of propylene oxide unit per mole and 10 g of a 10% aque~ls sodi~ alkyl aryl sulp~lonate solution in 183 g of water is aclded -to the latex. The mi~YtUre is acidified with 20 % -by ~7eight aqueous maleic acid.
pH-value 8 7 6 5 4 3 2 Coagulation point (C) (~) (x) 44 43 42 42 40 (x) no coagulation Without the adclition of amrnonia, the mi~ture is not heat-sensitive after aciclification.
E~MPLE 12 Following the proceclures of E~ample 1, a mix-tllre or 2.6 g of 25% by weight of a~leous ammonia and 3 g of an isopropanol-3o a~ine alkoxylated with 10 ~oles of propylene oxlde~its pe7-mole in 19~L.4 ~ of water is added ~o -the la-te~. T}le muxture is acidiiied with 20~ by weight a~leous ~leic acld.
p~l-Y~l~lc~ ~ 7 G 5 'L 3 `' Coa~ulatloll poirlt (C) (x) ~7 1L2 'LO 3~ 3~ 36 (x) no cocaglllat-ion Wit~lout the acldition of aDm~orlia~ the mi~tllre is not 3~3 heat-sensitive after acidi-fication.
E~MPLE l3 Followlng the procedures of Example l, a solu-tion of 2.4 g of 25~ by weight a~leous a~ncnia and 4 g of dodecyl amine co-aIkoxylated with 1Q moles of ethylene oxide ~its ~nd lO ~oles of propylene oxide in 193.6 ~ of water is added to the latex. Coagulation point at pH 3: 38C.
If, in a comparison tes-t, no a~mQnia is added, the mix-ture is not heat-sensitive after acidification.
E~IPLE l~
A solution of 0 8 g of cyclohe~yl amine and 5 g of an oleyl amine ethoxylated with 20 moles of ethylene oxide units per mole in 64.2 g o~ water is added to 250 parts by weight of 40% by w~ight latex of a copolymer of 64 % by weight of butadiene, 31 /0 by weight of acrylonitrile, 3.5 /0 by weight of N-methylol acrylamide and l.5 /0 by weigh-t of acrylamide. A storable mi~ture is obtained.
The mixture thus obtained is adjusted to pH 3 with 10~ by weight ac~lec~s maleic acid, acetic acid or succinic acid and its coagulation point determined. Coagulation point:
44C.
If no e-thoxylated oleyl amine is added, the mixtuIe coagulates immediately aEter acidifica-tion. If, in contrast, no cyclohe~yl a~ine is added, the mixture is no-t heat-sensitive after acidification.
EXAMPLE l5 Following the procedures of Example l4, a ~i~ture of 4 g of a 25~ by weight ac~eous ammonia solution, 3 g of an isopropanolamine propoxyla-ted wi-th 25 moles of propylene oxide units psr mole and 61 g of water is added to the latex.
r~he r~xtu.re is acidi~ied with 20~ ~y weight maleic acid. Co-agula-tion poirlt nt p~I 3: ~5C.
Witholl-t the aclclitioll of nl~noll:ia, -the ~ ture is not hea t-s~llsit:i~e .
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A mixture comprising from 2 to 30 parts by weight of at least one member selected from the group consisting of ammonia, monoamines other than aminopolyethers and polyamines other than polyaminopolyethers and from 70 to 98 parts by weight of at least one member selected from the group consisting of aminopolyether-based non-ionic surfactants and polyether-based non-ionic surfactants.
2. A mixture as claimed in claim 1 wherein said monoamine or polyamine is employed and is water-soluble.
3. A mixture as claimed in claim 1 wherein said aminopoly-ether-based non-ionic surfactant is employed, said aminopolyether being one that is obtainable by polyalkoxylating an aliphatic or aromatic monoamine or polyamine.
4. A mixture as claimed in claim 3 wherein the aminopolyether contains from 3 to 50 ethylene oxide units.
5. A mixture as claimed in claim 3 wherein the aminopolyether contains from 3 to 40 propylene oxide units.
6. A mixture as claimed in claim 1 containing as the polyether-based non-ionic surfactant, a polyalkoxylate of an alcohol, an aliphatic carboxylic acid, an aliphatic carboxylic acid amide, an alkyl sulphonic acid amide, an alkylated phenol, an alkylated naphthols or a hydroxydiphenyl.
7. A mixture as claimed in claim 1 containing as the polyether-based non-ionic surfactant, an alkylene oxide block polymer.
8. A mixture as claimed in claim 6 wherein the polyalkoxylate contains from 3 to 50 ethylene oxide units.
9. A mixture as claimed in claim 6 wherein the polyalkoxylate contains from 3 to 30 propylene oxide units.
10. A process for heat-sensitising a natural or synthetic latex in which a latex containing the mixture claimed in claim 1 is adjusted to a pH-value below 7.
11. A process as claimed in claim 10 wherein the latex contains from 0.01 to 4 % by weight, based on the polymer content, of ammonia, monoamine or polyamine, and from 0.5 to 10 %
by weight, based on the polymer content, of aminopolyether-based non-ionic surfactant or polyether-based non-ionic surfactant.
by weight, based on the polymer content, of aminopolyether-based non-ionic surfactant or polyether-based non-ionic surfactant.
12. A process as claimed in claim 11 wherein the latex contains from 0.05 to 2.5% by weight, based on the polymer content, of ammonia, monamine or polyamine, and from 1 to 5 %
by weight, based on the polymer content, of aminopolyether-based non-ionic surfactant.
by weight, based on the polymer content, of aminopolyether-based non-ionic surfactant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792905651 DE2905651A1 (en) | 1979-02-14 | 1979-02-14 | MIXTURE OF AMINES AND POLYAETHER COMPOUNDS, THEIR PRODUCTION AND USE AS A HEAT-SENSITIZING AGENT |
| DEP2905651.7 | 1979-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142338A true CA1142338A (en) | 1983-03-08 |
Family
ID=6062924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000345458A Expired CA1142338A (en) | 1979-02-14 | 1980-02-12 | Mixture of amines and polyether compounds its production and its use as a heat stabiliser |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0016324B1 (en) |
| JP (1) | JPS55110197A (en) |
| AT (1) | ATE3152T1 (en) |
| BR (1) | BR8000861A (en) |
| CA (1) | CA1142338A (en) |
| DE (2) | DE2905651A1 (en) |
| ES (1) | ES488530A0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4535111A (en) * | 1983-08-20 | 1985-08-13 | Bayer Aktiengesellschaft | Heat sensitizing agents, the production and use thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3036373A1 (en) * | 1980-09-26 | 1982-05-13 | Bayer Ag, 5090 Leverkusen | MIXTURE OF ALKOXYLATED POLYAMINES AND POLYETHER COMPOUNDS, THE PRODUCTION AND USE THEREOF AS A HEAT-SENSITIZING AGENT |
| US4499264A (en) * | 1983-06-27 | 1985-02-12 | Texaco Inc. | Preparation of amino polyols |
| US5461104A (en) * | 1994-01-21 | 1995-10-24 | Shell Oil Company | Process for making water-based latexes of block copolymers |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969289A (en) * | 1971-03-15 | 1976-07-13 | General Latex And Chemical Corporation | One-part foamable latex composition |
| US3878152A (en) * | 1972-12-29 | 1975-04-15 | Basf Ag | Heat-sensitization of anionic and non-ionic aqueous polymer dispersions |
| DE2226269C2 (en) * | 1972-05-30 | 1984-09-27 | Basf Ag, 6700 Ludwigshafen | Heat sensitization of anionic and nonionic aqueous polymer dispersions |
| FR2308646A1 (en) * | 1975-04-23 | 1976-11-19 | Rhone Poulenc Ind | HYDROPHILIC POLYURETHANNE AND ITS APPLICATION |
| US4102841A (en) * | 1975-11-28 | 1978-07-25 | The B. F. Goodrich Company | Heat sensitive latices |
-
1979
- 1979-02-14 DE DE19792905651 patent/DE2905651A1/en not_active Withdrawn
-
1980
- 1980-02-04 DE DE8080100542T patent/DE3062854D1/en not_active Expired
- 1980-02-04 EP EP80100542A patent/EP0016324B1/en not_active Expired
- 1980-02-04 AT AT80100542T patent/ATE3152T1/en not_active IP Right Cessation
- 1980-02-12 CA CA000345458A patent/CA1142338A/en not_active Expired
- 1980-02-12 JP JP1490580A patent/JPS55110197A/en active Pending
- 1980-02-13 BR BR8000861A patent/BR8000861A/en unknown
- 1980-02-13 ES ES488530A patent/ES488530A0/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4535111A (en) * | 1983-08-20 | 1985-08-13 | Bayer Aktiengesellschaft | Heat sensitizing agents, the production and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55110197A (en) | 1980-08-25 |
| ES8103131A1 (en) | 1981-02-16 |
| BR8000861A (en) | 1980-10-29 |
| EP0016324B1 (en) | 1983-04-27 |
| ATE3152T1 (en) | 1983-05-15 |
| DE2905651A1 (en) | 1980-08-21 |
| ES488530A0 (en) | 1981-02-16 |
| EP0016324A1 (en) | 1980-10-01 |
| DE3062854D1 (en) | 1983-06-01 |
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