CA1107874A - Stable heat-sensitive latex mixtures - Google Patents
Stable heat-sensitive latex mixturesInfo
- Publication number
- CA1107874A CA1107874A CA296,455A CA296455A CA1107874A CA 1107874 A CA1107874 A CA 1107874A CA 296455 A CA296455 A CA 296455A CA 1107874 A CA1107874 A CA 1107874A
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- Prior art keywords
- heat
- weight
- integer
- polymer
- stabiliser
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
- C08L21/02—Latex
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
STABLE HEAT-SENSITIVE LATEX MIXTURES
Abstract of the Disclosure A heat-sensitised polymer latex mixture containing from 0.05 to 10 % by weight, based on the polymer, of a heat sensitiser, and as stabiliser from 0.05 to 10 % by weight, based on the polymer of a polyether or a mixture of poly-ethers corresponding to the general formula (I):
Abstract of the Disclosure A heat-sensitised polymer latex mixture containing from 0.05 to 10 % by weight, based on the polymer, of a heat sensitiser, and as stabiliser from 0.05 to 10 % by weight, based on the polymer of a polyether or a mixture of poly-ethers corresponding to the general formula (I):
Description
~7~374 Heat-sensitive latex mixtures are known which are produced from heat-sensitisable polymer latices which in turn may be produced by emulsion polymerisation. Their heat sensitisation characteristics and agents suitable for this purpose are described, for example, in German Patents Nos.
1,268,828; 1,494,037 and in US Patent No. 3,484,394. One process for the production of heat-sensitisable, synthetic rubber latices is described in German Patent No. 1,243,394.
Heat-sensitised latex mixtures can be used for impregnating non-wovens and for the production of hollow bodies (for example gloves) by the immersion process.
However, conventional heat-sensitised latex mixtures are not sufficiently stable during processing. In many cases, the mechanical stability of the heat-sensitised latices is inadequate so that undesirable deposits are formed on guide rollers or between squeezing rollers during processing.
In general, non-ionic emulsifiers are added to the latex mixtures in order to improve their mechanical stability, but in order to obtain adequate stabilities, considerable quantities have to be added. This generally has an adverse effect upon heat sensitisability, in other words relatively large quantities of heat stabilisers are required for adjusting a predetermined coagulation temperature.
Le A 17 819 - 2 -~7874 The present invention is based on the discovery that heat-sensitised latex mixtures achieve better mechanical stability when they contain certain polyethers. Accordingly, the present invention provides a heat-sensitised synthetic polymer latex obtained by the emulsion polymerisation of one or more olefinically unsaturated monomers and containing from 0.05 to 10% by weight, based on the polymer, of a heat sen-sitiser, characterised in that said latex also contains a stabiliser in an amount of from 0.05 to 10% by weight, based on the polymer, said stabiliser being a polyether or a mix-ture of polyethers corresponding to the general formula (I):
R [ - (0-CH-CH)x-(O-CH2-CH)y~O~R4]n (I) Rl R2 R3 in which R represents optionally aryl-substituted alkyl or cyclo-alkyl radicals;
Rl, R2 and R3 independently of one another represent hydrogen, methyl, chloromethyl, ethyl or phenyl, with the proviso that Rl, R2 and R3 cannot all simultaneously represent hydrogen and, where _ = 0, Rl and R2 cannot simultaneously represent hydrogen;
R4 represents hydrogen or an aliphatic, cycloaliphatic or aromatic acyl radical containing from 1 to 30 carbon atoms;
x is an integer from 5 to 100;
_ is 0 or an integer from 1 to 50; and _ is an integer from 1 to 10.
In preferred polyethers or polyether mixtures, R represents an alkyl or cycloalkyl radical containing from
1,268,828; 1,494,037 and in US Patent No. 3,484,394. One process for the production of heat-sensitisable, synthetic rubber latices is described in German Patent No. 1,243,394.
Heat-sensitised latex mixtures can be used for impregnating non-wovens and for the production of hollow bodies (for example gloves) by the immersion process.
However, conventional heat-sensitised latex mixtures are not sufficiently stable during processing. In many cases, the mechanical stability of the heat-sensitised latices is inadequate so that undesirable deposits are formed on guide rollers or between squeezing rollers during processing.
In general, non-ionic emulsifiers are added to the latex mixtures in order to improve their mechanical stability, but in order to obtain adequate stabilities, considerable quantities have to be added. This generally has an adverse effect upon heat sensitisability, in other words relatively large quantities of heat stabilisers are required for adjusting a predetermined coagulation temperature.
Le A 17 819 - 2 -~7874 The present invention is based on the discovery that heat-sensitised latex mixtures achieve better mechanical stability when they contain certain polyethers. Accordingly, the present invention provides a heat-sensitised synthetic polymer latex obtained by the emulsion polymerisation of one or more olefinically unsaturated monomers and containing from 0.05 to 10% by weight, based on the polymer, of a heat sen-sitiser, characterised in that said latex also contains a stabiliser in an amount of from 0.05 to 10% by weight, based on the polymer, said stabiliser being a polyether or a mix-ture of polyethers corresponding to the general formula (I):
R [ - (0-CH-CH)x-(O-CH2-CH)y~O~R4]n (I) Rl R2 R3 in which R represents optionally aryl-substituted alkyl or cyclo-alkyl radicals;
Rl, R2 and R3 independently of one another represent hydrogen, methyl, chloromethyl, ethyl or phenyl, with the proviso that Rl, R2 and R3 cannot all simultaneously represent hydrogen and, where _ = 0, Rl and R2 cannot simultaneously represent hydrogen;
R4 represents hydrogen or an aliphatic, cycloaliphatic or aromatic acyl radical containing from 1 to 30 carbon atoms;
x is an integer from 5 to 100;
_ is 0 or an integer from 1 to 50; and _ is an integer from 1 to 10.
In preferred polyethers or polyether mixtures, R represents an alkyl or cycloalkyl radical containing from
2 to 10 carbon atoms;
Rl ~nd R3 represent hydrogen;
R2 represents methyl;
R4 represents hydrogen or an aliphatic acyl radical with 10 to 22 carbon atoms;
x is an integer from 10 to 50;
y is 0 or an integer from 1 to 25; and 10 n is an integer from 1 to 6.
Compounds in which y assumes values of 0 to 10 are particularly preferred.
The radical R4 may represent either hydrogen or an acyl radical, both alternatives having significance.
The polvethers which are used as stabilisers in accordance with the invention are produced by polyalkoxylating monohydric or polyhydric alcohols and optionally esterifying the products formed either completely or in part with carboxylic acids in known manner.
Monohydric or polyhydric alcohols suitable for use in the synthesis of the polyethers according to the invention are saturated or unsaturated aliphatic or cycloaliphatic mono-hydroxy compounds, for example methanol, ethanol, propanol, isopropanol, butanols, amyl alcohols, hexanols, octanols, dodecanols, stearyl alcohol, allyl alcohol, oleyl alcohol, cyclohexanol and benzyl alcohol, polyhydric alcohols, for example, hexitols, such as sorbitol or mannitol, but preferably Le A 17 ~19 - 4 -~787~
ethylene glycol, propylene glycol, butane diols, neopentyl glycol, 2-ethyl-1,3-propane diol and other hexane diols, 1,4-dihydroxymethyl cyclohexane, perhydrobisphenol-A, 2,2~-bis-[4-(2-hydroxyethyl)-phenyl]-propane, 2,2'-bis-[4-(2-hydroxypropoxy)-phenyl]-propane and, with particular preference, trimethylol ethane, trimethylol propane, glycerol and pentaerythritol.
For producing the polyethers according to the invention, the monohydric or polyhydric aclohols are polyalkoxylated with an alkylene oxide or, in stages, with two different alkylene oxides. Alkylene oxides suitable for use in cases where alkoxylation is carried out in a single stage are propylene oxide, 1,2- and 2,3-epoxy butane, isobutylene oxide, 2,3-epoxy pentane, epichlorhydrin and styrene oxide. Where alkoxylation is carried out in two stages, the above-mentioned alkylene oxides are suitable for use in the first stage, whilst ethylene oxide or propylene oxide in particular is used in the second stage. Where alkoxylation is carried out in a single stage, the alcohols are preferably alkoxylated with propylene oxide, whereas in the two-stage process, the alcohols are preferably reacted first with propylene oxide and then with ethylene oxide. It is, of course, also possible to carry out the reaction first with ethylene oxide and then with propylene oxide.
In addition to the block polymers, it is also possible to use copolymeric polyethers for stabilisationS for example products produced by alkoxylating the alcohols with a mixture Le A 17 819 - 5 -i~7~7~
of propylene and ethylene oxide containing up to 20 mole %
of ethylene oxide, or products which, in a first alkoxylation stage, contain up to 20 mole /0 of ethylene oxide in addition to propylene oxide and, in a second stage, up to 20 mole /0 of propylene oxide in addition to ethylene oxide. Although these products are suitable for stabilisation in accordance with the invention, they are not preferred.
The alkoxylated alcohols may be used either as such or may be completely or partly esterified with carboxylic acid.
Suitable carboxylic acids for esterification are aliphatic and aromatic carboxylic acids containing from 1 to 30 carbon atoms, but preferably saturated or unsaturated aliphatic carboxylic acids containing from 10 to 22 carbon atoms, for example capric acid, lauric acid, palmitic acid, stearic acid, behenic acid, ricinoleic acid, ricinene acid, linoleic acid, linolenic acid or abietic acid or mixtures of saturated and/or unsaturated aliphatic carboxylic acids of the type which accumulate during the oxidation of paraffins and during the synthesis of oxo compounds and which are obtained by the hydrolysis of vegetable or animal fats.
In many cases, the polyethers are only sparingly soluble in water, if at all, and frequently are also only sparingly emulsifiable therein. By contrast, their activity increases with good distribution. Accordingly, in order to improve their emulsifiability, it is often advisable to add to the polyethers conventional anion-active or non-ionic emulsifiers, for example, alkylaryl sulphonates, alkyl sulphates, fatty acid Le A 17 819 - 6 -8~4 salts, fatty acid ethoxylates, alkyl phenol ethoxylates, aryl phenol ethoxylates, aryl phenyl ethoxylates, fatty acid ethoxylates or the like. Additions of from 1 to 30%~ based on the polyethers, are generally sufficient.
Heat-sensitised latex mixtures which contain the poly-ethers defined above are characterised by their high mechanical stability. In many cases, their stability can be further increased by adding ammonia in quantities of from 0.1 to 1 /0 by weight, based on polymer. When the heat sensitiser is added, no undesirable deposits of coagulate are formed.
In all conventional heat-sensitised latices, the improvement in stability can be obtained by adding the polyether stabilisers on completion of polymerisation. Examples of the production of heat-sensitisable latices such as these may be found in German Patent No. 1,243,394 and in German Offenlegungsschri~ts Nos. 2,232,526 and 2,005,974. However, stable latex emulsions are also obtained when the polyethers are added right at the beginning of or during polymerisation of the latex.
In order to produce the heat-sensitisable stable latices themselves, conventional olefinically unsaturated monomers may be polymerised in aqueous emulsion. Suitable monomers include any radically polymerisable olefinically unsaturated compounds, for example ethylene, butadiene, isoprene, acrylonitrile, styrene, divinyl benzene, a-methyl styrene, methacrylonitrile, acrylic acid, methacrylic acid, 2-chloro-1,3-butadiene, esters of acrylic acid and methacrylic acid with Cl-C8-alcohols or polyols, acrylamide, methacrylamide, N-methyloltmeth) Le A 17 819 7 acrylamide, acrylamido- and methacrylamide-N-methylol methyl ethers, itaconic acid, maleic acid, fumaric acid, diesters and semiesters of unsaturated dicarboxylic acids, vinyl chloride, vinylacetate, vinylidene chloride, which may be used either individually or in combination with one another.
The polymerisation reaction is carried out in the presence of emulsifiers, for which purpose the usual non-ionic or anionic emulsifiers may be used either individually or in combination with one another. The total quantity of emulsifier amounts to between 0.1 and 10 /0 by weight, based on the monomers.
Where the polyethers are added during the actual polymerisation reaction, they are advantageously used in combination with standard commercial-grade emulsifiers, for example in combination with alkali sulphonates or sulphates of C12-C18-hydrocarbons or of alkylated aromatic compounds, or with non-ionic surfactants or with salts of fatty acids or resinic acids or with salts of alkyl esters of sulphosuccinic acid.
The quantity of polyether stabiliser added amounts to between 0.05 and 10 /0 by weight, based on monomers, where it is added to the latex during the actual polymerisation reaction, or to between 0.05 and 10 /0 by weight, based on polymer, where it is added to the latex on completion of polymerisation.
The emulsion polymerisation reaction may be initiated with radical formers, preferably with organoperoxide compounds, which are used in quantities of from 0.01 to 2 % by weight, based on monomers. Depending upon the monomer combination, small quantities of regulators, for example mercaptans, halogenated Le A 17 819 - 8 -11C~7874 hydrocarbons, may also be used in order to reduce the molecular weight of the polymer. The emulsion polymerisation reaction may be carried out in two ways: the entire quantity of monomers and most of the aqueous phase containing the emulsifiers may be initially introduced, the polymerisation reaction initiated by adding the initiator and the rest of the aqueous phase added either continuously or in portions during the polymerisation reaction. The "monomer input" technique may also be used.
In this case, only part of the monomers and the aqueous phase containing the emulsifier is initially introduced and the rest of the monomers and aqueous phase added either continuously or in portions, according to the conversion, after the polymerisation reaction has been initiated. The proportion of monomer subsequently added may be pre-emulsified in the aqueous phase. Both processes are known.
Additives may be introduced into the heat-sensitisable latices before or during processing. Thus, acid donors which are added in addition to the sensitiser promote coagulatability by reducing the coagulation temperature. Examples of other suitable additives are dyes, pigments, fillers, thickeners, electrolytes, antiagers, water-soluble resins or vulcanisation chemicals.
After their production, the heat-sensitisable latices are heat-sensitised by the addition of heat sensitisers in quantities of from 0.05 to 10 ~ by weight, based on the polymer.
In this connection, it has been found that latices containing the polyether stabilisers according to the invention are Le A 17 819 - 9 -7~4 particularly stable so that when heat sensitisers are added to these latices no ¢oagulation occurs. Suitable heat sensitisers are inter alia organopolysiloxanes, for example according to German Auslegeschrift No. 1,268,828; German Offenlegungsschrift No. 1,494,037 and US Patent Specification No. 3,484,394. Other suitable heat sensitisers are polyvinyl methyl ethers, polyglycol ethers, polyether thioethers, polyol-N-vinyl caprolactam and/or polycarboxylic acids.
The heat-sensitised latex mixtures according to the invention may be used, for example, for bonding non-wovens consisting of synthetic or natural fibres. Examples are non-wovens of cotton , rayon staple, wool, polyamides, polyesters, polyacrylonitrile, glass fibres, mineral wool, asbestos wool or metal filaments.
The following stabilisers are mentioned as examples:
A) The polyether produced by alkoxylating trimethylol propane first with 41 moles of propylene oxide and then with 10 moles of ethylene oxide, OH-number: 57.
B) Oleic acid ester of polyether A
To produce this product, 500 g of polyether A are esterified with 94 g of oleic acid (acid number 203) at a temperature of 180 to 190C. Approximate~ 9 ml of water are distilled off over a period of 16 hours (acid number of the ester 15.4).
C) The polyether produced by alkoxylating trimethylol propane initially with 84 moles of propylene oxide and subsequently with 23 moles of ethylene oxide, OH-number 28.
Le A 17 819 -10 -1~7i~7~
D) The polyether produced by alkoxylating trimethylol propane initially with 70 moles of propylene oxide and subsequently with 14 moles of ethylene oxide, OH-number 35.
E) The polyether produced by alkoxylating pentaerythritol initially with 84 moles of propylene oxide and subsequently with 20 moles of butylene oxide, OH-number 37.5.
F) Polypropylene glycol produced from 1 mole of propylene glycol and 33 moles of propylene oxide, OH-number 58.3.
G) The polyether produced by propoxylating trimethylol propane with 50 moles of propylene oxide, OH-number 58.2.
H) Peanut oil fatty acid ester of polyether E:
To produce this product, 498 g of polyether E are esterified with 88 g of peanut oil fatty acid (acid number 203) at a temperature of 180 - 190C. Approximately 6 ml of water are distilled off over a period of 14 hours (acid number of the ester 17.2).
I) Soya oil fatty acid of polyether C:
To produce this product, 500 g of polyether C are esterified with 61.7 g of soya oil fatty acid (acid number 215.5) at a temperature of 180 to 190C. Approximately 4.5 ml of water are distilled off over a period of 20 hours (acid number of the ester 15.1).
K) Polypropylene glycol produced by propoxylating propylene oxide with 23 moles of propylene oxide, OH-number 78.2.
L) The polyether produced by propoxylating methanol with 17 moles of propylene oxide, OH-number: 57.1.
M) The polyether produced by alkoxylating sorbitol first with -Le A 17 819 - 11 -ii78~4 170 moles of propylene oxide and then with 45 moles of ethylene oxide, OH-numbe:r 28.
2L0 parts by weight of a 47 % latex of the copolymer of 5 62~o by weight of butadiene, 34.0 % by weight of acrylonitrile and 4.0 % by weight of methacrylic acid, 27.5 parts by weight of a vulcanisation paste consisting of 0.5 % by weight of colloidal sulphur, 0.5 % by weight of zinc-N,N'-diethyl dithiocarbamate, 3.75 % by weight of zinc mercaptobenzthiazole, 12.5 % by weight of zinc oxide, 12.5 %
by weight of titanium di.oxide and 70.25 % by weight of a 5 %
aqueous solution of a condensation product of naphthalene sulphonic acid with formaldehyde, 2.5 parts by weight of a 25 % ammonia solution, 15 130 parts by weight of water, 1 part by weight of organopolysiloxane (Coagulant WSR, a product of Bayer AG) and 1 part by weight of a stabiliser according to Example 1, were stirred together. The coagulation point of the mixture was 20 determined immediately, 1 hour, 2 hours, 1 day and 7 days after production.
The coagulation point of the latex mixture was determined as follows:
Approximately 10 g of the heat-sensitised mixture were 25 weighed into a glass beaker which was then introduced into a water bath having a constant temperature of 80C. The coagulation behaviour and increase in temperature were followed while the mixture was uniformly stirred with a thermometer. The Le A 17 819 - 12 -, coagulation point of the mixture was the temperature at which a complete and final separation of polymer and aqueous phase occurred.
Table Stabiliser Coa~ulation temperature (C ) after:
immediately lh 2h 1 day 7 days I ~9 40 40 40 41 _ This Example demonstrates the dependence of the coagulation temperature upon the quantity of stabiliser used. Mixtures were produced in accordance with Example 2, stabiliser A being used in other quantities in addition to 1 part by weight.
Table Quantity of Coa~ulation t _ ,ure (~ ') aiter stabiliser immediately ~ ~ j 1 day j 7 days 25 oo 5 37 3378 378 388 40 2.5 72 73 73 75 77 Le A 17 819 - 13 -~ 7~7~
Mixtures were produced in accordance with Example 2. In contrast to Example 2, however, 2 parts by weight of organo-polysiloxane (Coagulant WS) and different quantities by weight 5 of stabiliser A were used.
Table Quantity of Coa~ulation temperature (C) after stabiliser = lh 2h ~ l I~YL~
0.5 34 33 34 35 33 l . o 36 37 37 39 38 2.0 40 40 40 41 43
Rl ~nd R3 represent hydrogen;
R2 represents methyl;
R4 represents hydrogen or an aliphatic acyl radical with 10 to 22 carbon atoms;
x is an integer from 10 to 50;
y is 0 or an integer from 1 to 25; and 10 n is an integer from 1 to 6.
Compounds in which y assumes values of 0 to 10 are particularly preferred.
The radical R4 may represent either hydrogen or an acyl radical, both alternatives having significance.
The polvethers which are used as stabilisers in accordance with the invention are produced by polyalkoxylating monohydric or polyhydric alcohols and optionally esterifying the products formed either completely or in part with carboxylic acids in known manner.
Monohydric or polyhydric alcohols suitable for use in the synthesis of the polyethers according to the invention are saturated or unsaturated aliphatic or cycloaliphatic mono-hydroxy compounds, for example methanol, ethanol, propanol, isopropanol, butanols, amyl alcohols, hexanols, octanols, dodecanols, stearyl alcohol, allyl alcohol, oleyl alcohol, cyclohexanol and benzyl alcohol, polyhydric alcohols, for example, hexitols, such as sorbitol or mannitol, but preferably Le A 17 ~19 - 4 -~787~
ethylene glycol, propylene glycol, butane diols, neopentyl glycol, 2-ethyl-1,3-propane diol and other hexane diols, 1,4-dihydroxymethyl cyclohexane, perhydrobisphenol-A, 2,2~-bis-[4-(2-hydroxyethyl)-phenyl]-propane, 2,2'-bis-[4-(2-hydroxypropoxy)-phenyl]-propane and, with particular preference, trimethylol ethane, trimethylol propane, glycerol and pentaerythritol.
For producing the polyethers according to the invention, the monohydric or polyhydric aclohols are polyalkoxylated with an alkylene oxide or, in stages, with two different alkylene oxides. Alkylene oxides suitable for use in cases where alkoxylation is carried out in a single stage are propylene oxide, 1,2- and 2,3-epoxy butane, isobutylene oxide, 2,3-epoxy pentane, epichlorhydrin and styrene oxide. Where alkoxylation is carried out in two stages, the above-mentioned alkylene oxides are suitable for use in the first stage, whilst ethylene oxide or propylene oxide in particular is used in the second stage. Where alkoxylation is carried out in a single stage, the alcohols are preferably alkoxylated with propylene oxide, whereas in the two-stage process, the alcohols are preferably reacted first with propylene oxide and then with ethylene oxide. It is, of course, also possible to carry out the reaction first with ethylene oxide and then with propylene oxide.
In addition to the block polymers, it is also possible to use copolymeric polyethers for stabilisationS for example products produced by alkoxylating the alcohols with a mixture Le A 17 819 - 5 -i~7~7~
of propylene and ethylene oxide containing up to 20 mole %
of ethylene oxide, or products which, in a first alkoxylation stage, contain up to 20 mole /0 of ethylene oxide in addition to propylene oxide and, in a second stage, up to 20 mole /0 of propylene oxide in addition to ethylene oxide. Although these products are suitable for stabilisation in accordance with the invention, they are not preferred.
The alkoxylated alcohols may be used either as such or may be completely or partly esterified with carboxylic acid.
Suitable carboxylic acids for esterification are aliphatic and aromatic carboxylic acids containing from 1 to 30 carbon atoms, but preferably saturated or unsaturated aliphatic carboxylic acids containing from 10 to 22 carbon atoms, for example capric acid, lauric acid, palmitic acid, stearic acid, behenic acid, ricinoleic acid, ricinene acid, linoleic acid, linolenic acid or abietic acid or mixtures of saturated and/or unsaturated aliphatic carboxylic acids of the type which accumulate during the oxidation of paraffins and during the synthesis of oxo compounds and which are obtained by the hydrolysis of vegetable or animal fats.
In many cases, the polyethers are only sparingly soluble in water, if at all, and frequently are also only sparingly emulsifiable therein. By contrast, their activity increases with good distribution. Accordingly, in order to improve their emulsifiability, it is often advisable to add to the polyethers conventional anion-active or non-ionic emulsifiers, for example, alkylaryl sulphonates, alkyl sulphates, fatty acid Le A 17 819 - 6 -8~4 salts, fatty acid ethoxylates, alkyl phenol ethoxylates, aryl phenol ethoxylates, aryl phenyl ethoxylates, fatty acid ethoxylates or the like. Additions of from 1 to 30%~ based on the polyethers, are generally sufficient.
Heat-sensitised latex mixtures which contain the poly-ethers defined above are characterised by their high mechanical stability. In many cases, their stability can be further increased by adding ammonia in quantities of from 0.1 to 1 /0 by weight, based on polymer. When the heat sensitiser is added, no undesirable deposits of coagulate are formed.
In all conventional heat-sensitised latices, the improvement in stability can be obtained by adding the polyether stabilisers on completion of polymerisation. Examples of the production of heat-sensitisable latices such as these may be found in German Patent No. 1,243,394 and in German Offenlegungsschri~ts Nos. 2,232,526 and 2,005,974. However, stable latex emulsions are also obtained when the polyethers are added right at the beginning of or during polymerisation of the latex.
In order to produce the heat-sensitisable stable latices themselves, conventional olefinically unsaturated monomers may be polymerised in aqueous emulsion. Suitable monomers include any radically polymerisable olefinically unsaturated compounds, for example ethylene, butadiene, isoprene, acrylonitrile, styrene, divinyl benzene, a-methyl styrene, methacrylonitrile, acrylic acid, methacrylic acid, 2-chloro-1,3-butadiene, esters of acrylic acid and methacrylic acid with Cl-C8-alcohols or polyols, acrylamide, methacrylamide, N-methyloltmeth) Le A 17 819 7 acrylamide, acrylamido- and methacrylamide-N-methylol methyl ethers, itaconic acid, maleic acid, fumaric acid, diesters and semiesters of unsaturated dicarboxylic acids, vinyl chloride, vinylacetate, vinylidene chloride, which may be used either individually or in combination with one another.
The polymerisation reaction is carried out in the presence of emulsifiers, for which purpose the usual non-ionic or anionic emulsifiers may be used either individually or in combination with one another. The total quantity of emulsifier amounts to between 0.1 and 10 /0 by weight, based on the monomers.
Where the polyethers are added during the actual polymerisation reaction, they are advantageously used in combination with standard commercial-grade emulsifiers, for example in combination with alkali sulphonates or sulphates of C12-C18-hydrocarbons or of alkylated aromatic compounds, or with non-ionic surfactants or with salts of fatty acids or resinic acids or with salts of alkyl esters of sulphosuccinic acid.
The quantity of polyether stabiliser added amounts to between 0.05 and 10 /0 by weight, based on monomers, where it is added to the latex during the actual polymerisation reaction, or to between 0.05 and 10 /0 by weight, based on polymer, where it is added to the latex on completion of polymerisation.
The emulsion polymerisation reaction may be initiated with radical formers, preferably with organoperoxide compounds, which are used in quantities of from 0.01 to 2 % by weight, based on monomers. Depending upon the monomer combination, small quantities of regulators, for example mercaptans, halogenated Le A 17 819 - 8 -11C~7874 hydrocarbons, may also be used in order to reduce the molecular weight of the polymer. The emulsion polymerisation reaction may be carried out in two ways: the entire quantity of monomers and most of the aqueous phase containing the emulsifiers may be initially introduced, the polymerisation reaction initiated by adding the initiator and the rest of the aqueous phase added either continuously or in portions during the polymerisation reaction. The "monomer input" technique may also be used.
In this case, only part of the monomers and the aqueous phase containing the emulsifier is initially introduced and the rest of the monomers and aqueous phase added either continuously or in portions, according to the conversion, after the polymerisation reaction has been initiated. The proportion of monomer subsequently added may be pre-emulsified in the aqueous phase. Both processes are known.
Additives may be introduced into the heat-sensitisable latices before or during processing. Thus, acid donors which are added in addition to the sensitiser promote coagulatability by reducing the coagulation temperature. Examples of other suitable additives are dyes, pigments, fillers, thickeners, electrolytes, antiagers, water-soluble resins or vulcanisation chemicals.
After their production, the heat-sensitisable latices are heat-sensitised by the addition of heat sensitisers in quantities of from 0.05 to 10 ~ by weight, based on the polymer.
In this connection, it has been found that latices containing the polyether stabilisers according to the invention are Le A 17 819 - 9 -7~4 particularly stable so that when heat sensitisers are added to these latices no ¢oagulation occurs. Suitable heat sensitisers are inter alia organopolysiloxanes, for example according to German Auslegeschrift No. 1,268,828; German Offenlegungsschrift No. 1,494,037 and US Patent Specification No. 3,484,394. Other suitable heat sensitisers are polyvinyl methyl ethers, polyglycol ethers, polyether thioethers, polyol-N-vinyl caprolactam and/or polycarboxylic acids.
The heat-sensitised latex mixtures according to the invention may be used, for example, for bonding non-wovens consisting of synthetic or natural fibres. Examples are non-wovens of cotton , rayon staple, wool, polyamides, polyesters, polyacrylonitrile, glass fibres, mineral wool, asbestos wool or metal filaments.
The following stabilisers are mentioned as examples:
A) The polyether produced by alkoxylating trimethylol propane first with 41 moles of propylene oxide and then with 10 moles of ethylene oxide, OH-number: 57.
B) Oleic acid ester of polyether A
To produce this product, 500 g of polyether A are esterified with 94 g of oleic acid (acid number 203) at a temperature of 180 to 190C. Approximate~ 9 ml of water are distilled off over a period of 16 hours (acid number of the ester 15.4).
C) The polyether produced by alkoxylating trimethylol propane initially with 84 moles of propylene oxide and subsequently with 23 moles of ethylene oxide, OH-number 28.
Le A 17 819 -10 -1~7i~7~
D) The polyether produced by alkoxylating trimethylol propane initially with 70 moles of propylene oxide and subsequently with 14 moles of ethylene oxide, OH-number 35.
E) The polyether produced by alkoxylating pentaerythritol initially with 84 moles of propylene oxide and subsequently with 20 moles of butylene oxide, OH-number 37.5.
F) Polypropylene glycol produced from 1 mole of propylene glycol and 33 moles of propylene oxide, OH-number 58.3.
G) The polyether produced by propoxylating trimethylol propane with 50 moles of propylene oxide, OH-number 58.2.
H) Peanut oil fatty acid ester of polyether E:
To produce this product, 498 g of polyether E are esterified with 88 g of peanut oil fatty acid (acid number 203) at a temperature of 180 - 190C. Approximately 6 ml of water are distilled off over a period of 14 hours (acid number of the ester 17.2).
I) Soya oil fatty acid of polyether C:
To produce this product, 500 g of polyether C are esterified with 61.7 g of soya oil fatty acid (acid number 215.5) at a temperature of 180 to 190C. Approximately 4.5 ml of water are distilled off over a period of 20 hours (acid number of the ester 15.1).
K) Polypropylene glycol produced by propoxylating propylene oxide with 23 moles of propylene oxide, OH-number 78.2.
L) The polyether produced by propoxylating methanol with 17 moles of propylene oxide, OH-number: 57.1.
M) The polyether produced by alkoxylating sorbitol first with -Le A 17 819 - 11 -ii78~4 170 moles of propylene oxide and then with 45 moles of ethylene oxide, OH-numbe:r 28.
2L0 parts by weight of a 47 % latex of the copolymer of 5 62~o by weight of butadiene, 34.0 % by weight of acrylonitrile and 4.0 % by weight of methacrylic acid, 27.5 parts by weight of a vulcanisation paste consisting of 0.5 % by weight of colloidal sulphur, 0.5 % by weight of zinc-N,N'-diethyl dithiocarbamate, 3.75 % by weight of zinc mercaptobenzthiazole, 12.5 % by weight of zinc oxide, 12.5 %
by weight of titanium di.oxide and 70.25 % by weight of a 5 %
aqueous solution of a condensation product of naphthalene sulphonic acid with formaldehyde, 2.5 parts by weight of a 25 % ammonia solution, 15 130 parts by weight of water, 1 part by weight of organopolysiloxane (Coagulant WSR, a product of Bayer AG) and 1 part by weight of a stabiliser according to Example 1, were stirred together. The coagulation point of the mixture was 20 determined immediately, 1 hour, 2 hours, 1 day and 7 days after production.
The coagulation point of the latex mixture was determined as follows:
Approximately 10 g of the heat-sensitised mixture were 25 weighed into a glass beaker which was then introduced into a water bath having a constant temperature of 80C. The coagulation behaviour and increase in temperature were followed while the mixture was uniformly stirred with a thermometer. The Le A 17 819 - 12 -, coagulation point of the mixture was the temperature at which a complete and final separation of polymer and aqueous phase occurred.
Table Stabiliser Coa~ulation temperature (C ) after:
immediately lh 2h 1 day 7 days I ~9 40 40 40 41 _ This Example demonstrates the dependence of the coagulation temperature upon the quantity of stabiliser used. Mixtures were produced in accordance with Example 2, stabiliser A being used in other quantities in addition to 1 part by weight.
Table Quantity of Coa~ulation t _ ,ure (~ ') aiter stabiliser immediately ~ ~ j 1 day j 7 days 25 oo 5 37 3378 378 388 40 2.5 72 73 73 75 77 Le A 17 819 - 13 -~ 7~7~
Mixtures were produced in accordance with Example 2. In contrast to Example 2, however, 2 parts by weight of organo-polysiloxane (Coagulant WS) and different quantities by weight 5 of stabiliser A were used.
Table Quantity of Coa~ulation temperature (C) after stabiliser = lh 2h ~ l I~YL~
0.5 34 33 34 35 33 l . o 36 37 37 39 38 2.0 40 40 40 41 43
3.0 43 43 44 46 45
4.0 48 48 49 49 5 This Examples also demonstrates the dependence oi the coagulation temperature upon the quantity of stabiliser used.
250.0 parts by weight of a 40 ~ latex of the copolymer of 60.0 % by weight of butadiene, 34.0 ~ by weight of acrylonitrile, 2.0 /0 by weight of acrylic acid, 2.0 ~ by weight of methacrylamide and 2.0 % by weight of methacrylamido-N-methylol methyl ether, x parts by weight of stabiliser A (see Example 1), 38.0 parts by weight of water and 2.0 parts by weight of organopolysiloxane (Coagulant WSR , a product of Bayer AG) were combined.
The coagulation points of the mixtures were determined immediately, 30 minutes, 1 day and 6 days after production.
The coagulation points were measured by the method described in Example 2.
Le A 17 819 - 14 -11(:17~74 Table : Quantity of Coa~ulation t emperature ( ,) after stabiliser immediately 30 mins. 1 da~ 7 days A used (g) : 5 5 43 44 45 47 :~ 2.0 68 68 7 7 ::
,,:.
~r `";':
.,.,. ,:
i','~
. ;
~
~:
, ~:
'` ' ~' ' '~i ' '.'X~
'"
Le A 17 819 - 15 -`:
~- , : . :
:, : .: . ::
250.0 parts by weight of a 40 ~ latex of the copolymer of 60.0 % by weight of butadiene, 34.0 ~ by weight of acrylonitrile, 2.0 /0 by weight of acrylic acid, 2.0 ~ by weight of methacrylamide and 2.0 % by weight of methacrylamido-N-methylol methyl ether, x parts by weight of stabiliser A (see Example 1), 38.0 parts by weight of water and 2.0 parts by weight of organopolysiloxane (Coagulant WSR , a product of Bayer AG) were combined.
The coagulation points of the mixtures were determined immediately, 30 minutes, 1 day and 6 days after production.
The coagulation points were measured by the method described in Example 2.
Le A 17 819 - 14 -11(:17~74 Table : Quantity of Coa~ulation t emperature ( ,) after stabiliser immediately 30 mins. 1 da~ 7 days A used (g) : 5 5 43 44 45 47 :~ 2.0 68 68 7 7 ::
,,:.
~r `";':
.,.,. ,:
i','~
. ;
~
~:
, ~:
'` ' ~' ' '~i ' '.'X~
'"
Le A 17 819 - 15 -`:
~- , : . :
:, : .: . ::
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A heat-sensitised synthetic polymer latex obtained by the emulsion polymerisation of one or more olefinically unsaturated monomers and containing from 0.05 to 10% by weight, based on the polymer, of a heat sensitiser, char-acterised in that said latex also contains a stabiliser in an amount of from 0.05 to 10% by weight, based on the polymer, said stabiliser being a polyether or a mixture of polyethers corresponding to the general formula (I):
(I) in which R represents an optionally aryl-substituted alkyl or cycloalkyl radical;
R1, R2 and R3 independently of one another represent hydrogen, methyl, chloromethyl, ethyl or phenyl, with the proviso that the radicals R1, R2 and R3 cannot simultaneously represent hydrogen and, where y = 0, R1 and R2 cannot simultaneously represent hydrogen;
R4 represents hydrogen or an aliphatic, cycloaliphatic or aromatic acyl radical containing from 1 to 30 carbon atoms;
x is an integer from 5 to 100;
y is 0 or an integer from 1 to 50; and n is an integer from 1 to 10.
(I) in which R represents an optionally aryl-substituted alkyl or cycloalkyl radical;
R1, R2 and R3 independently of one another represent hydrogen, methyl, chloromethyl, ethyl or phenyl, with the proviso that the radicals R1, R2 and R3 cannot simultaneously represent hydrogen and, where y = 0, R1 and R2 cannot simultaneously represent hydrogen;
R4 represents hydrogen or an aliphatic, cycloaliphatic or aromatic acyl radical containing from 1 to 30 carbon atoms;
x is an integer from 5 to 100;
y is 0 or an integer from 1 to 50; and n is an integer from 1 to 10.
2. A heat-sensitised polymer latex as claimed in Claim 1, which contains as a stabiliser a polyether or a mixture of polyethers corresponding to general formula (I) in which R represent an alkyl or cycloalkyl radical containing from 2 to 10 carbon atoms;
R1 and R3 represent hydrogen;
R2 represents methyl;
R4 represents hydrogen or an aliphatic acyl radical containing from 10 to 22 carbon atoms;
x is an integer from 10 to 50;
y is 0 or an integer from 1 to 25; and n is an integer from 1 to 6.
R1 and R3 represent hydrogen;
R2 represents methyl;
R4 represents hydrogen or an aliphatic acyl radical containing from 10 to 22 carbon atoms;
x is an integer from 10 to 50;
y is 0 or an integer from 1 to 25; and n is an integer from 1 to 6.
3. A heat-sensitised polymer latex as claimed in claim 1 or 2, wherein y is 0 or an integer from 1 to 10.
4. A method of stabilising a heat-sensitive synthetic polymer latex wherein an olefinically unsaturated monomer or monomer mixture is subjected to polymerisation and wherein prior to, during or after the polymerisation from 0.05 to 10% by weight based on the monomer or polymer, of a stabiliser of general formula (I) as defined in claim 1 are added and wherein following polymerisation from 0.05 to 10% by weight, based on the polymer, of a heat sensitiser are added to the polymer latex.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2705555.6 | 1977-02-10 | ||
| DE19772705555 DE2705555A1 (en) | 1977-02-10 | 1977-02-10 | STABLE HEAT-SENSITIVE LATEX MIXTURES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1107874A true CA1107874A (en) | 1981-08-25 |
Family
ID=6000815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA296,455A Expired CA1107874A (en) | 1977-02-10 | 1978-02-08 | Stable heat-sensitive latex mixtures |
Country Status (9)
| Country | Link |
|---|---|
| BE (1) | BE863801A (en) |
| BR (1) | BR7800776A (en) |
| CA (1) | CA1107874A (en) |
| DE (1) | DE2705555A1 (en) |
| ES (1) | ES466824A1 (en) |
| FR (1) | FR2380321A1 (en) |
| GB (1) | GB1558951A (en) |
| IT (1) | IT7847948A0 (en) |
| NL (1) | NL7801449A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55102653A (en) * | 1979-01-30 | 1980-08-06 | Japan Synthetic Rubber Co Ltd | Production of water-containing polymer molding |
| CA1242362A (en) * | 1983-04-19 | 1988-09-27 | Douglas C. Edwards | Aramid fibre-polymer mixtures and process for production |
| GB8402191D0 (en) * | 1984-01-27 | 1984-02-29 | Ici Plc | Coating process |
| DE3530301A1 (en) * | 1985-08-24 | 1987-02-26 | Henkel Kgaa | ANTI-FOAM AGENT FOR POLYMER DISPERSIONS (I) |
| GB2273294B (en) * | 1992-11-11 | 1997-06-11 | Jujo Paper Co Ltd | Aqueous polyolefin resin composition |
| ES2140926T3 (en) * | 1996-03-11 | 2000-03-01 | Goodyear Tire & Rubber | PROCESS TO PREPARE HEAT SENSITIZABLE LATEX AND LATEX. |
| CA2301928A1 (en) * | 1999-04-30 | 2000-10-30 | Gerald Owen Schulz | Latex for aggregate treatment |
| US6242524B1 (en) * | 1999-06-02 | 2001-06-05 | The Goodyear Tire & Rubber Company | Binder for non-woven fabric |
| WO2023180263A1 (en) * | 2022-03-21 | 2023-09-28 | Schill + Seilacher Struktol Gmbh | Rubber composition containing additive and use thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3484394A (en) * | 1967-06-07 | 1969-12-16 | Gen Electric | Heat-sensitive latex |
| GB1545104A (en) * | 1975-05-07 | 1979-05-02 | Bayer Ag | Process for the production of concentrated polychloroprene latices |
-
1977
- 1977-02-10 DE DE19772705555 patent/DE2705555A1/en not_active Withdrawn
-
1978
- 1978-02-06 GB GB4641/78A patent/GB1558951A/en not_active Expired
- 1978-02-07 IT IT7847948A patent/IT7847948A0/en unknown
- 1978-02-08 CA CA296,455A patent/CA1107874A/en not_active Expired
- 1978-02-08 NL NL7801449A patent/NL7801449A/en not_active Application Discontinuation
- 1978-02-09 BE BE185031A patent/BE863801A/en not_active IP Right Cessation
- 1978-02-09 BR BR7800776A patent/BR7800776A/en unknown
- 1978-02-09 ES ES466824A patent/ES466824A1/en not_active Expired
- 1978-02-10 FR FR7803872A patent/FR2380321A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| ES466824A1 (en) | 1978-10-01 |
| BR7800776A (en) | 1978-11-28 |
| FR2380321A1 (en) | 1978-09-08 |
| IT7847948A0 (en) | 1978-02-07 |
| GB1558951A (en) | 1980-01-09 |
| NL7801449A (en) | 1978-08-14 |
| BE863801A (en) | 1978-08-09 |
| DE2705555A1 (en) | 1978-08-17 |
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| MKEX | Expiry |