CA1153140A - Process for the production of emulsifier-free rubber latices - Google Patents
Process for the production of emulsifier-free rubber laticesInfo
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- CA1153140A CA1153140A CA000331439A CA331439A CA1153140A CA 1153140 A CA1153140 A CA 1153140A CA 000331439 A CA000331439 A CA 000331439A CA 331439 A CA331439 A CA 331439A CA 1153140 A CA1153140 A CA 1153140A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- Polymers & Plastics (AREA)
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
Abstract of the Disclosure A process for the production of an emulsifier-free rubber latex from (meth)acrylic acid and a mixture of acyclic conuugated dienes and arylvinyl monomers and/or (meth)acrylonitrile, wherein an aqueous emul-sion is prepared by adding at least part of the (meth) acrylic acid, part of the diene and other monomers to water, polymerisation is initiated by the addition of an aqueous solution of a peroxodisulphate and is carried out in a first stage at a pH-value of from 3.5 to 7 until at least 50 % of the monomers have been polymerised, the rest of the monomers and of initiator are added in one or more further stages, and polymerisation is continued at a pH-value of from 3.5 to 7 until at least 50 % of the monomers and, in the final stage, until from 85 to 100 % of the mono-mers have been polymerised.
Le A 18 151 -
Le A 18 151 -
Description
1~53~40 This invention relates to a process for the production of emulsifier-free rubber latices of (meth) acrylic acid and acyclic conjugated dienes together with arylvinyl monomers and/or (meth)acrylonitrile.
In conventional emulsion polymerisation processes, the monomers are normally polymerised in the presence of an initiator which releases free radicals and an emulsifier which keeps the polymer particles formed in dispersion. However, the presence of emulsifiers frequently leads to difficulties in the processing of the latices owing to inadequate mechanical stability or to foam formation and results in a reduction in the wet strength of the coatings produced with dispersions such as these or of the substrates treated with them and in reduced adhesion of the binder to the substrates.
It i8 known that the stability of rubber latices can be increased and the sensitivity of the $ilms to water can be reduced by carrying out the emulsion polymerisation reaction in the presence of emulsifiers which are incorporated into the polymer, such as for example semiesters of maleic acid and fatty alcohols (German Auslegeschrift No. 1,011,548) or 4-styrene undecanoic acid (US Patent No. 2,868,755). This internal binding of the surface-active substances considerably reduces the sensitivity of the latices to shear forces by co~parison with latices of the type in which the polymer particles are stabilised by the adsorption of emulsifier molecules.
The incorporation o~ monomers containing strongly 3o dissociating groups also gives rubber latices which show considerably greater stability than rubber latices containing adsorbed surface-active substances. Stable emulsifier-free rubber latices of this type are obtained ~e A 18 151 , ~, ,~ ~
, , . . ~ . ~
~15~V
by copolymerising monomers containing sulphonic acid groups in aqueous emulsion, for example by the incorporation o~ 4-styrene sulphonic acid (US Patents Nos. 2,913,429 and 3,306,871~ or by means oi esters o~ acrylic or methacrylic acid and 2-hydroxyethane sulphonic acid, such as for example 2-sulphoethyl acrylate (US Patent No. 2,914,499).
In this way, the latex particles are stabilised by sulphonate groups which provide ~or an adequate charge on the suriace oi the particles.
It is known irom US Patent No. 3,784,498 that emulsi~ier-free carboxylated rubber latices can be obtained by initially preparing a latex ~rom the total quantity o~ the ethylenically unsaturated carboxylic acid and part of the water-insoluble monomers at a pH-value o~ irom about 2 to 4, adding the rest of the monomers after the pH-value has been adjusted to between 7 and 10 and continuing polymerisation until a complete conversion is obtained. This measure drastically increases the dissociation o~ the carboxyl groups so that the polymer particle9 are adequately stabilised by the carboxylate groups during the second polymerisation stage, thus avoiding coagulation. ~owever, the necessary increase in the pH-value from 2-4 to 7-10, ior which aqueous ammonia ispre~erably used, complicates the process because the ammo~nia has to be added slowly and carefully and, in many cases, leads to considerable coagulate ~ormation.
It has now been found that emulsi~ier-free carboxylated latices can be obtained from (meth)acrylic acid, dienes and arylvinyl monomers and/or (meth)acrylo-nitrile using a peroxodisulphate as radical initiator, providing at least part of the (meth)acrylic acid, part - of the diene and other monomers are polymerised at a pH-value oi irom 3.5 to 7, the rest of the monomers : Le A 18 151 1 ~S31 ~0 are added in one or more stages and the polymerisation reaction is continued at this pH-value until at least 50 % of the monomers have been polymerised and, in the final stage, until from 85 to lO0 % of the monomers have been polymerised. The process according to the invention enables corresponding rubber latices to be produced without using emulsifiers.
~ he process is generally carried out by initially introducing water and at least part of the (meth)acrylic acid, part of the conjugated diene and arylvinyl monomers and/or (meth)acrylonitrile into a reactor and initiating the polymerisation reaction at a temperature above 70C
and preierably at a temperature of from 75 to ~5C by the addition of an aqueous, preferably ammoniacal peroxodisulphate solution, the ammonia content of which is measured in such a way that polymerisation takes place at a pH-value of ~rom 3.5 to 7. Polymerisation is continued up to a conversion oi at least 50 % and, depending on the pressure conditions in the reactorand the required final concentration, more monomer and, optionally, (meth)acrylic acid and more aqueous, preferably ammoniacal, peroxodisulphate solution are added in batches so that the polymerisation reaction is continued at a pH-value of from 3.5 to 7.
In general, two or three stages are su~iicient Yor this polymerisation reaction, although more polymerisation stages are also possible. In each polymerisation stage, polymerisation is continued up to a conversion of at least 50 /0. In the ~inal stage, polymerisation is continued up to a con~ersion of from ~5 to lO0 /0 o$ the monomers.
A latex having a solids content o~ from 30 to 65 /0 by weight and preierably from 40 to 60 % by weight is obtained.
Both organic and also inorganic bases, for example Le A 18 151 1~53~0 NaHC03, ammonia or triethylamine, are suitable for adjusting the pH to a value of from 3.5 to 7 during the polymerisation reaction. It is preferred to use aliphatic amines and ammonia, ammonia being particularly preferred.
The total quantity of the peroxodisulphate used as initiator in the process according to the invention amounts to between 0.5 and 3.0 parts by weight, based on the total quantity of monomers. Suitable initiators are salts of peroxodisulphuric acid, such as sodium, potassium or, pre~erably, ammonium peroxodisulphate.
In one preferred embodiment, the individual poly-merisation stages are initiated by the addition of an aqueous ammoniacal peroxodisulphate solution which simultaneously adjusts the pH to a value of 3.5 - 7.
Surprisingly, the process according to the invention can be applied so universally that the ratio of conjugated diene to arylvinyl monomer and/or (meth)acrylonitrile can be varied within very wide limits. Accordingly, it is possible in accordance with the invention to produce from the above-mentioned monomers rubber latices which contain from lO to 90 parts by weight of one or more acyclic conjugated dienes containing from 4 to 9 carbon atoms, from 0 to 90 parts by weight of one or more arylvinyl monomers containing from 8 to 12 carbon atoms and/or ~rom 0 to 50 parts by weight of (meth)acrylonitrile, the sum of the last two components amounting to between lO and 90 parts by weight.
Accordingly, the present invention provides a process for the production of an emulsifier-free rubber latex from l to 6 parts by weight oi ~meth)acrylic acid and 94 to 99 ; parts by weight o~ a mixture of lO to 90 parts by weight ; of one or more acyclic conjugated dienes containing ~rom ~e A 18 151 ~531~0 4 to 9 carbon atoms and 10 to 90 parts by weight of one or more arylvinyl monomers containing from 8 to 12 carbon atoms and/or (meth)acrylonitrile, the quantity oi (meth)acrylonitrile amounting to at most 50 parts by weight, characterised in that a) an aqueous emulsion i9 prepared by adding at least part of the (meth)acrylic acid, part of the diene and other monomers to water, b) the polymerisation reaction is initiated by the addition of an aqueous ~olution of a peroxodi-sulphate, c) polymerisation is carried out in a first stage at a pH-value of from 3.5 to 7 and at a temperature above 70C until at least 50 /0 of the monomers have been polymerised, d) the rest o~ the monomers and more aqueous peroxo-di~ulphate solution are added in one or more ; ~urther stages, and e) polymerisation is continued at a pH-value oi from 3.5 to 7 and at a temperature above 70C until at least 50 % of the monomers have been converted and, in the ~inal stage, until irom 85 to 100 /0 of the monomers have been converted.
Suitable acyclic conjugated dienes containing from 4 to 9 carbon atoms are, ~or example, 1,3-butadiene,
In conventional emulsion polymerisation processes, the monomers are normally polymerised in the presence of an initiator which releases free radicals and an emulsifier which keeps the polymer particles formed in dispersion. However, the presence of emulsifiers frequently leads to difficulties in the processing of the latices owing to inadequate mechanical stability or to foam formation and results in a reduction in the wet strength of the coatings produced with dispersions such as these or of the substrates treated with them and in reduced adhesion of the binder to the substrates.
It i8 known that the stability of rubber latices can be increased and the sensitivity of the $ilms to water can be reduced by carrying out the emulsion polymerisation reaction in the presence of emulsifiers which are incorporated into the polymer, such as for example semiesters of maleic acid and fatty alcohols (German Auslegeschrift No. 1,011,548) or 4-styrene undecanoic acid (US Patent No. 2,868,755). This internal binding of the surface-active substances considerably reduces the sensitivity of the latices to shear forces by co~parison with latices of the type in which the polymer particles are stabilised by the adsorption of emulsifier molecules.
The incorporation o~ monomers containing strongly 3o dissociating groups also gives rubber latices which show considerably greater stability than rubber latices containing adsorbed surface-active substances. Stable emulsifier-free rubber latices of this type are obtained ~e A 18 151 , ~, ,~ ~
, , . . ~ . ~
~15~V
by copolymerising monomers containing sulphonic acid groups in aqueous emulsion, for example by the incorporation o~ 4-styrene sulphonic acid (US Patents Nos. 2,913,429 and 3,306,871~ or by means oi esters o~ acrylic or methacrylic acid and 2-hydroxyethane sulphonic acid, such as for example 2-sulphoethyl acrylate (US Patent No. 2,914,499).
In this way, the latex particles are stabilised by sulphonate groups which provide ~or an adequate charge on the suriace oi the particles.
It is known irom US Patent No. 3,784,498 that emulsi~ier-free carboxylated rubber latices can be obtained by initially preparing a latex ~rom the total quantity o~ the ethylenically unsaturated carboxylic acid and part of the water-insoluble monomers at a pH-value o~ irom about 2 to 4, adding the rest of the monomers after the pH-value has been adjusted to between 7 and 10 and continuing polymerisation until a complete conversion is obtained. This measure drastically increases the dissociation o~ the carboxyl groups so that the polymer particle9 are adequately stabilised by the carboxylate groups during the second polymerisation stage, thus avoiding coagulation. ~owever, the necessary increase in the pH-value from 2-4 to 7-10, ior which aqueous ammonia ispre~erably used, complicates the process because the ammo~nia has to be added slowly and carefully and, in many cases, leads to considerable coagulate ~ormation.
It has now been found that emulsi~ier-free carboxylated latices can be obtained from (meth)acrylic acid, dienes and arylvinyl monomers and/or (meth)acrylo-nitrile using a peroxodisulphate as radical initiator, providing at least part of the (meth)acrylic acid, part - of the diene and other monomers are polymerised at a pH-value oi irom 3.5 to 7, the rest of the monomers : Le A 18 151 1 ~S31 ~0 are added in one or more stages and the polymerisation reaction is continued at this pH-value until at least 50 % of the monomers have been polymerised and, in the final stage, until from 85 to lO0 % of the monomers have been polymerised. The process according to the invention enables corresponding rubber latices to be produced without using emulsifiers.
~ he process is generally carried out by initially introducing water and at least part of the (meth)acrylic acid, part of the conjugated diene and arylvinyl monomers and/or (meth)acrylonitrile into a reactor and initiating the polymerisation reaction at a temperature above 70C
and preierably at a temperature of from 75 to ~5C by the addition of an aqueous, preferably ammoniacal peroxodisulphate solution, the ammonia content of which is measured in such a way that polymerisation takes place at a pH-value of ~rom 3.5 to 7. Polymerisation is continued up to a conversion oi at least 50 % and, depending on the pressure conditions in the reactorand the required final concentration, more monomer and, optionally, (meth)acrylic acid and more aqueous, preferably ammoniacal, peroxodisulphate solution are added in batches so that the polymerisation reaction is continued at a pH-value of from 3.5 to 7.
In general, two or three stages are su~iicient Yor this polymerisation reaction, although more polymerisation stages are also possible. In each polymerisation stage, polymerisation is continued up to a conversion of at least 50 /0. In the ~inal stage, polymerisation is continued up to a con~ersion of from ~5 to lO0 /0 o$ the monomers.
A latex having a solids content o~ from 30 to 65 /0 by weight and preierably from 40 to 60 % by weight is obtained.
Both organic and also inorganic bases, for example Le A 18 151 1~53~0 NaHC03, ammonia or triethylamine, are suitable for adjusting the pH to a value of from 3.5 to 7 during the polymerisation reaction. It is preferred to use aliphatic amines and ammonia, ammonia being particularly preferred.
The total quantity of the peroxodisulphate used as initiator in the process according to the invention amounts to between 0.5 and 3.0 parts by weight, based on the total quantity of monomers. Suitable initiators are salts of peroxodisulphuric acid, such as sodium, potassium or, pre~erably, ammonium peroxodisulphate.
In one preferred embodiment, the individual poly-merisation stages are initiated by the addition of an aqueous ammoniacal peroxodisulphate solution which simultaneously adjusts the pH to a value of 3.5 - 7.
Surprisingly, the process according to the invention can be applied so universally that the ratio of conjugated diene to arylvinyl monomer and/or (meth)acrylonitrile can be varied within very wide limits. Accordingly, it is possible in accordance with the invention to produce from the above-mentioned monomers rubber latices which contain from lO to 90 parts by weight of one or more acyclic conjugated dienes containing from 4 to 9 carbon atoms, from 0 to 90 parts by weight of one or more arylvinyl monomers containing from 8 to 12 carbon atoms and/or ~rom 0 to 50 parts by weight of (meth)acrylonitrile, the sum of the last two components amounting to between lO and 90 parts by weight.
Accordingly, the present invention provides a process for the production of an emulsifier-free rubber latex from l to 6 parts by weight oi ~meth)acrylic acid and 94 to 99 ; parts by weight o~ a mixture of lO to 90 parts by weight ; of one or more acyclic conjugated dienes containing ~rom ~e A 18 151 ~531~0 4 to 9 carbon atoms and 10 to 90 parts by weight of one or more arylvinyl monomers containing from 8 to 12 carbon atoms and/or (meth)acrylonitrile, the quantity oi (meth)acrylonitrile amounting to at most 50 parts by weight, characterised in that a) an aqueous emulsion i9 prepared by adding at least part of the (meth)acrylic acid, part of the diene and other monomers to water, b) the polymerisation reaction is initiated by the addition of an aqueous ~olution of a peroxodi-sulphate, c) polymerisation is carried out in a first stage at a pH-value of from 3.5 to 7 and at a temperature above 70C until at least 50 /0 of the monomers have been polymerised, d) the rest o~ the monomers and more aqueous peroxo-di~ulphate solution are added in one or more ; ~urther stages, and e) polymerisation is continued at a pH-value oi from 3.5 to 7 and at a temperature above 70C until at least 50 % of the monomers have been converted and, in the ~inal stage, until irom 85 to 100 /0 of the monomers have been converted.
Suitable acyclic conjugated dienes containing from 4 to 9 carbon atoms are, ~or example, 1,3-butadiene,
2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, piperylene, 2-neopentyl-1,3-butadiene and other substituted dienes, such as ior example 2-chloro-1,3-butadiene (chloroprene), 2-cyano-1,3-butadiene and substituted straight-chain conjugated pentadienes and straight-chain or branched chain hexadienes. Its ability to copolymerise particularly well with arylvinyl monomers makes 1,3-butadiene the preferred monomer.
Le A 18 151 .
Suitable arylvinyl monomers are those in which the vinyl group, optionally alkyl-substituted in the ~-position, i9 directly attached to an aromatic nucleus consisting of from 6 to lO carbon atoms3 for example styrene and substituted styrenes, such as 4-methyl styrene, 3-methyl styrene, 2,4-dimethyl styrene, 2,4-diethyl styrene, 4-isopropyl styrene, 4-chlorostyrene, 2,4-dichlorostyrene, divinyl benzene, ~-methyl styrene and vinyl naphthalene. For reasons o$ availability and by virtue o$ its ability to copolymerise ef$ectively, particularly with l,3-butadiene, styrene is the preferred monomer.
Up to 25 parts by weight o$ the non-dissociating monomers may be replaced by one or more monomers which can be copolymerised with the above-mentioned monomers.
Monomers such as these are acrylic and/or methacrylic acid esters o$ alcohols containing up to 8 carbon atoms and also diesters oY alkane diols and ~,~-monoethylenically unsaturated monocarboxylic acids, such as ethylene glycol diacrylate and l,4-butane diol diacrylate, and amides of ~,~-monoethylenically unsaturated mono- and di-carboxylic acids, such as acrylamide and methacrylamide. Further comonomers ~hich may be used for the purposes o$ the invention include vinyl esters o$ carboxylic acids containing $rom l to 18 carbon atoms, particularly vinyl acetate and vinyl propionate, vinyl chloride and vinylidene chloride, vinyl ethers, such as vinyl methyl ether, vinyl ketones, such as vinyl ethyl ketone, and heterocyclic monovinyl compounds, such as vinyl pyridine.
In addition to the a~ove-mentioned monomers, known chain-transfér agents may be used ior in$1uencing the properties of the copolymers. Suitable chain-trans$er Le A_18 151 ~5~3~ ~0 agents are long-chain alkyl mercaptans such as, for example, tert.-dodecyl mercaptan, mercaptocarboxylic acids, such as thioglycolic acid, lower dialkyl di-xanthogenates, carbon tetrabromide and bromoethyl benzene. The quantity in which the chain transfer agent is used is determined inter alia by its effectiveness and also by the quantity in which the diene is used and may readily be selected by the expert.
As already mentioned, the process according to the invention is a polymerisation process which i8 carried out in two or more stages, the number of stages being determined by the pressure conditions in the reactor and by the required final concentration of the latex. Depending on the number of polymerisation stages, about hal~ the total of non-dissociating monomers is initially introduced in a two-stage operation, about a third in a three-stage operation, and so on. Accordingly, the monomers are added in substantially equal portions commensurate with the number of stages. ~his also applies to the (meth)acrylic acid, although it is also possible for the methacrylic acid to be completely introduced in the first stage alone.
In the first stage, the polymerisation reaction is carried out until a conversion of at least 50 /0 is obtained. In the majority of cases, complete poly-merisation in the first stage i9 unadvisable because, in many cases, this measure leads to the formation of deposits and microcoagulate. In the first stage, polymerisation is preferably carried out up to a conversion of from 70 to 85 /0 by weight, after which a second batch of the non-dissociating monomers is ~- added, more aqueous peroxodisulphate solution is intro-duced and polymerisation is continued at a pH-value of Le A 18 151 i ~153~ ~0 from ~.5 to 7. The addition of more acrylic and/or methacrylic acid is governed by the total quantity of the acid which may amount to between l and 6 parts by weight, based on the monomer total. Where only l part by weight is used, the total quantity of (meth)acrylic acid i9 introduced in the first stage, although where a larger quantity is used, it is generally more favourable to distribute the acid between the individual polymeris-ation stages. In the second polymerisation stage and in each following polymerisation stage, polymerisation is continued until all the monomers then present have been polymerised up to a conversion of at least 50 %. Finally, in the last stage, polymerisation is continued until from 85 to lO0 /0 oi' the monomers have been converted.
In many cases, it is su~ficient to carry out the process in only two stages, in the first of which polymerisation is carried out up to a conversion of at least 50 /0 and in the second of which polymerisation is continued up to a conversion of from 85 to lO0 %. The late~ may then be freed from residual monomers in known manner at a pH-value of from 6 to 8 and, to increase its mechanical stability, may be adjusted to a pH-value of from about 8 to lO.
The process according to the invention gives emulsifier-free rubber latices which have extremely high stability with respect to chemical and mechanical influences, show very little foam formation during processing, are compatible with other emulsifier-free or emulsifier-containing latices and with liquid phenolic resins, and may readily be concentrated by the removal of water. The polymer films produced from these latices and articles produced with these dispersions show considerably improved resistance to water, dry and r ~
Le A 18 151 l~S3~V
harden more quickly, adhere much more firmly to the particular substrates and show far less discolouration by comparison with articles produced from dispersions containing even small quantities of emulsifiers. Polymer films and products wi*h improved resistance to water are obtained in particular from alkali-metal-free latices in the production of which ammonia is used for adjusting the pH-value and ammonium peroxodisulphate as initiator. ~he latices produced in accordance with the invention are surprisingly distinguished by their versatility in terms of practical application and may be used, for example, as a leather finish, for bonding non-woven fabrics, for impregnating and coating textile materials and papers, and for the production oi adhesives, printing inks and aqueous paint binder formulations.
The process according to the invention is illustrated by the ~ollowing Examples.
In a 40 litre stainless steel reactor equipped with a crossed-arms paddle stirrer, a solution of 120 g of ammonium peroxodisulphate and 30 ml of a 25 % aqueous ammonia solution in 500 g of water is added at 80C
to a mixture of 2500 g of 1,3-butadiene, 2400 g of styrene and lll g of 90 /0 methacrylic acid in 8750 g of water, followed by polymerisation at 80C until a solids concentration of approximately 20 % by weight is reached tafter 4 hours). In the meantime, the pH-value of the emulsion remains between 4.3 and 4.l. 2500 g of l,3-butadiene, 2400 g of styrene and lll g of 90 ~0 meth-acrylic acid are then added, followed by the additionof another 30 g of ammonium peroxodisulphate and 30 ml of a 25 % aqueous ammonia solution in 500 g of water to the emulsion, after which polymerisation is continued to Le A 1i3 151 ~lS~ V
10.5 hours at a temperature of 80C. During this second polymerisation phase, the pH-value of the emulsion remains between 4.~ and 4.6.
After a solids concentration of 50.5 % by weight has been reached, the polymerisation mixture is cooled to room temperature, 280 g of a 7 ~ diethyl hydroxylamine solution are added, and the latex i9 substantially neutralised with an aqueous ammonia solution and then freed from residual monomers. The pH is then adjusted to a value of 9.2 with aqueous ammonia solution. Deposits which only amount to 130 g (weighed moist) are then filtered off, leaving a latex having a solids content o~
49.6 ~, a particle diameter of from 320 to 340 nm and a surface tension of 47.2 mN/m.
This latex is suitable for the production of needle felt floor coverings and as a first-coat latex for stabilising tufted fabrics.
The following Comparison Examples illustrate the influence on polymerisation of the pH-value and the methacrylic acid.
COMPARISON EXAMPLE 1 (without ammonia) The procedure is as in Example 1, except that the aqueous ammonia solutions are not added in either of the two polymerisation phases. As a result, the first polymerisation phase is carried out at a pH-value of from 2.1 to 1.6 and a solids concentratio~ of 20 ~0 by weight is reached after akout 3.5 hours. In the second phase, the polymerisation time amounts to 11 hours for a pH value o~ from 1.5 to 1.4.
; 30 After a concentration of 49.7 /0 by weight has been reached, the polymerisation mixture is cooled, the polymerisation reaction is stopped, the lateæ is substantially neutralised with ammonia and then freed Le A 18 151 l~S3~.~0 _ 12 -~rom residual monomers in the same way as in Example 1.
Adjustment of the pH-value to 9.0 with dilute aqueous ammonia solution gives a latex having a solids concen-tration o~ 47.5 /0 by weight and containing considerable quantities of coagulate. The filtered latex has particle diameters oi irom about 280 to 310 nm and a suriace tension oi 48.3 mN/m.
COMPARISON EXAMPLE 2 (without m_thacrylic acid) In a 40 litre stainless steel autoclave equipped with a crossed-arms paddle stirrer, a mixture of 2500 g oi 1,3-butadiene and 2500 g of styrene in 11250 g of water is polymerised at 80C with a solution of 150 g o~
ammonium peroxodisulphate and 30 ml o~ a 25 % aqueous ammonia solution until a solids concentration o~
appro~imately 20 /0 by weight is reached (after 6.5 hours).
During this first polymerisation phase, the pH-value o$ the emulsion ialls ~rom 8.2 to 2.3. Another 2500 g oi 1,3-butadiene and 2500 g of styrene and an aqueous solution o$ 100 g oi ammonium peroxodisulphate and 30 ml oi 25 % aqueous ammonia solution are then added, after which polymerisation is continued for 20 hours at a pH-value falling from 8.0 to 1.7 until a solids concentrationo~ 44 /0 by weight is reached. Stopping oi the poly-merisation reaction and working up in the same way as in Example 1 leave a latex which has to be iiltered o~f irom a large quantity of coagulate.
COMPARISON EXAMPLE 3 (without ammonia and methacr~lic acid) ~ he procedure is as in Comparison Example 2, e~cept that no ammonia is added in either the first or the second polymerisation phase. As a result, the poly-merisation velocity decreases with a reduction in pH
- ~rom 2.4 to 1 4, so that a solids concentration o$ 19 /0 by weight is only reached a~ter 10 hours and a final concentration of 43.7 /0 by weight is only reached a~ter another 25 hours at a pH-value oi 1.0 despite reactivation with 20 g of ammonium peroxodisulphate in 100 g oi water Le A 18 151 ~lS~l~V
Le A 18 151 .
Suitable arylvinyl monomers are those in which the vinyl group, optionally alkyl-substituted in the ~-position, i9 directly attached to an aromatic nucleus consisting of from 6 to lO carbon atoms3 for example styrene and substituted styrenes, such as 4-methyl styrene, 3-methyl styrene, 2,4-dimethyl styrene, 2,4-diethyl styrene, 4-isopropyl styrene, 4-chlorostyrene, 2,4-dichlorostyrene, divinyl benzene, ~-methyl styrene and vinyl naphthalene. For reasons o$ availability and by virtue o$ its ability to copolymerise ef$ectively, particularly with l,3-butadiene, styrene is the preferred monomer.
Up to 25 parts by weight o$ the non-dissociating monomers may be replaced by one or more monomers which can be copolymerised with the above-mentioned monomers.
Monomers such as these are acrylic and/or methacrylic acid esters o$ alcohols containing up to 8 carbon atoms and also diesters oY alkane diols and ~,~-monoethylenically unsaturated monocarboxylic acids, such as ethylene glycol diacrylate and l,4-butane diol diacrylate, and amides of ~,~-monoethylenically unsaturated mono- and di-carboxylic acids, such as acrylamide and methacrylamide. Further comonomers ~hich may be used for the purposes o$ the invention include vinyl esters o$ carboxylic acids containing $rom l to 18 carbon atoms, particularly vinyl acetate and vinyl propionate, vinyl chloride and vinylidene chloride, vinyl ethers, such as vinyl methyl ether, vinyl ketones, such as vinyl ethyl ketone, and heterocyclic monovinyl compounds, such as vinyl pyridine.
In addition to the a~ove-mentioned monomers, known chain-transfér agents may be used ior in$1uencing the properties of the copolymers. Suitable chain-trans$er Le A_18 151 ~5~3~ ~0 agents are long-chain alkyl mercaptans such as, for example, tert.-dodecyl mercaptan, mercaptocarboxylic acids, such as thioglycolic acid, lower dialkyl di-xanthogenates, carbon tetrabromide and bromoethyl benzene. The quantity in which the chain transfer agent is used is determined inter alia by its effectiveness and also by the quantity in which the diene is used and may readily be selected by the expert.
As already mentioned, the process according to the invention is a polymerisation process which i8 carried out in two or more stages, the number of stages being determined by the pressure conditions in the reactor and by the required final concentration of the latex. Depending on the number of polymerisation stages, about hal~ the total of non-dissociating monomers is initially introduced in a two-stage operation, about a third in a three-stage operation, and so on. Accordingly, the monomers are added in substantially equal portions commensurate with the number of stages. ~his also applies to the (meth)acrylic acid, although it is also possible for the methacrylic acid to be completely introduced in the first stage alone.
In the first stage, the polymerisation reaction is carried out until a conversion of at least 50 /0 is obtained. In the majority of cases, complete poly-merisation in the first stage i9 unadvisable because, in many cases, this measure leads to the formation of deposits and microcoagulate. In the first stage, polymerisation is preferably carried out up to a conversion of from 70 to 85 /0 by weight, after which a second batch of the non-dissociating monomers is ~- added, more aqueous peroxodisulphate solution is intro-duced and polymerisation is continued at a pH-value of Le A 18 151 i ~153~ ~0 from ~.5 to 7. The addition of more acrylic and/or methacrylic acid is governed by the total quantity of the acid which may amount to between l and 6 parts by weight, based on the monomer total. Where only l part by weight is used, the total quantity of (meth)acrylic acid i9 introduced in the first stage, although where a larger quantity is used, it is generally more favourable to distribute the acid between the individual polymeris-ation stages. In the second polymerisation stage and in each following polymerisation stage, polymerisation is continued until all the monomers then present have been polymerised up to a conversion of at least 50 %. Finally, in the last stage, polymerisation is continued until from 85 to lO0 /0 oi' the monomers have been converted.
In many cases, it is su~ficient to carry out the process in only two stages, in the first of which polymerisation is carried out up to a conversion of at least 50 /0 and in the second of which polymerisation is continued up to a conversion of from 85 to lO0 %. The late~ may then be freed from residual monomers in known manner at a pH-value of from 6 to 8 and, to increase its mechanical stability, may be adjusted to a pH-value of from about 8 to lO.
The process according to the invention gives emulsifier-free rubber latices which have extremely high stability with respect to chemical and mechanical influences, show very little foam formation during processing, are compatible with other emulsifier-free or emulsifier-containing latices and with liquid phenolic resins, and may readily be concentrated by the removal of water. The polymer films produced from these latices and articles produced with these dispersions show considerably improved resistance to water, dry and r ~
Le A 18 151 l~S3~V
harden more quickly, adhere much more firmly to the particular substrates and show far less discolouration by comparison with articles produced from dispersions containing even small quantities of emulsifiers. Polymer films and products wi*h improved resistance to water are obtained in particular from alkali-metal-free latices in the production of which ammonia is used for adjusting the pH-value and ammonium peroxodisulphate as initiator. ~he latices produced in accordance with the invention are surprisingly distinguished by their versatility in terms of practical application and may be used, for example, as a leather finish, for bonding non-woven fabrics, for impregnating and coating textile materials and papers, and for the production oi adhesives, printing inks and aqueous paint binder formulations.
The process according to the invention is illustrated by the ~ollowing Examples.
In a 40 litre stainless steel reactor equipped with a crossed-arms paddle stirrer, a solution of 120 g of ammonium peroxodisulphate and 30 ml of a 25 % aqueous ammonia solution in 500 g of water is added at 80C
to a mixture of 2500 g of 1,3-butadiene, 2400 g of styrene and lll g of 90 /0 methacrylic acid in 8750 g of water, followed by polymerisation at 80C until a solids concentration of approximately 20 % by weight is reached tafter 4 hours). In the meantime, the pH-value of the emulsion remains between 4.3 and 4.l. 2500 g of l,3-butadiene, 2400 g of styrene and lll g of 90 ~0 meth-acrylic acid are then added, followed by the additionof another 30 g of ammonium peroxodisulphate and 30 ml of a 25 % aqueous ammonia solution in 500 g of water to the emulsion, after which polymerisation is continued to Le A 1i3 151 ~lS~ V
10.5 hours at a temperature of 80C. During this second polymerisation phase, the pH-value of the emulsion remains between 4.~ and 4.6.
After a solids concentration of 50.5 % by weight has been reached, the polymerisation mixture is cooled to room temperature, 280 g of a 7 ~ diethyl hydroxylamine solution are added, and the latex i9 substantially neutralised with an aqueous ammonia solution and then freed from residual monomers. The pH is then adjusted to a value of 9.2 with aqueous ammonia solution. Deposits which only amount to 130 g (weighed moist) are then filtered off, leaving a latex having a solids content o~
49.6 ~, a particle diameter of from 320 to 340 nm and a surface tension of 47.2 mN/m.
This latex is suitable for the production of needle felt floor coverings and as a first-coat latex for stabilising tufted fabrics.
The following Comparison Examples illustrate the influence on polymerisation of the pH-value and the methacrylic acid.
COMPARISON EXAMPLE 1 (without ammonia) The procedure is as in Example 1, except that the aqueous ammonia solutions are not added in either of the two polymerisation phases. As a result, the first polymerisation phase is carried out at a pH-value of from 2.1 to 1.6 and a solids concentratio~ of 20 ~0 by weight is reached after akout 3.5 hours. In the second phase, the polymerisation time amounts to 11 hours for a pH value o~ from 1.5 to 1.4.
; 30 After a concentration of 49.7 /0 by weight has been reached, the polymerisation mixture is cooled, the polymerisation reaction is stopped, the lateæ is substantially neutralised with ammonia and then freed Le A 18 151 l~S3~.~0 _ 12 -~rom residual monomers in the same way as in Example 1.
Adjustment of the pH-value to 9.0 with dilute aqueous ammonia solution gives a latex having a solids concen-tration o~ 47.5 /0 by weight and containing considerable quantities of coagulate. The filtered latex has particle diameters oi irom about 280 to 310 nm and a suriace tension oi 48.3 mN/m.
COMPARISON EXAMPLE 2 (without m_thacrylic acid) In a 40 litre stainless steel autoclave equipped with a crossed-arms paddle stirrer, a mixture of 2500 g oi 1,3-butadiene and 2500 g of styrene in 11250 g of water is polymerised at 80C with a solution of 150 g o~
ammonium peroxodisulphate and 30 ml o~ a 25 % aqueous ammonia solution until a solids concentration o~
appro~imately 20 /0 by weight is reached (after 6.5 hours).
During this first polymerisation phase, the pH-value o$ the emulsion ialls ~rom 8.2 to 2.3. Another 2500 g oi 1,3-butadiene and 2500 g of styrene and an aqueous solution o$ 100 g oi ammonium peroxodisulphate and 30 ml oi 25 % aqueous ammonia solution are then added, after which polymerisation is continued for 20 hours at a pH-value falling from 8.0 to 1.7 until a solids concentrationo~ 44 /0 by weight is reached. Stopping oi the poly-merisation reaction and working up in the same way as in Example 1 leave a latex which has to be iiltered o~f irom a large quantity of coagulate.
COMPARISON EXAMPLE 3 (without ammonia and methacr~lic acid) ~ he procedure is as in Comparison Example 2, e~cept that no ammonia is added in either the first or the second polymerisation phase. As a result, the poly-merisation velocity decreases with a reduction in pH
- ~rom 2.4 to 1 4, so that a solids concentration o$ 19 /0 by weight is only reached a~ter 10 hours and a final concentration of 43.7 /0 by weight is only reached a~ter another 25 hours at a pH-value oi 1.0 despite reactivation with 20 g of ammonium peroxodisulphate in 100 g oi water Le A 18 151 ~lS~l~V
3 --at a solids content of 40 /0 by weight. An unstable latex is obtained, coagulating spontaneously on completion of polymerisation.
COMPARISON EXAMPLE 4 (with methacrylic a _d) 2500 g of 1,3-butadiene~ 2400 g of styrene and 111 g of 90 % methacrylic acid in 250 g of water are added to 10,000 g of water, and polymerisation is initiated by the addition at 80C of a solution of 150 g of ammonium peroxodisulphate in 500 g of water. A solids concentration of 20 % by weight is reached after only 3.5 hours. The pH-value during the first polymerisation phase remains between 2.4 and 1.6. 2400 g of styrene, 2500 g Or 1,3-butadiene, 111 g of 90 /0 methacrylic acid and a solution of 100 g of ammonium peroxodisulphate in 500 g of water are then added. A solids concentration of 43.7 % by weight is reached after another 10 hours at a pH-value of 1~3. Stopping of the polymerisation reaction and working up in the same way as in Example 1 leaves a latex which, although stable, contains considerable quantities of coagulate.
In a 40 litre stainless steel reactor equipped with a crossed-arms paddle stirrer, a mi~ture of 1200 g of styrene and 1200 g of acrylonitrile, 2500 g of 1,3-butadiene and 111 g of 90 /0 methacrylic acid in 250 g Of water and 100 g of methacrylamide are polymerised at 75C in 12500 g of water with a solution of 50 g of ammonium peroxodisulphate in 500 g of water and 3~ ml of 25 oh aqueous ammonia solution. A solids concentration of 25.3 /0 by weight is reached after polymerisation rOr
COMPARISON EXAMPLE 4 (with methacrylic a _d) 2500 g of 1,3-butadiene~ 2400 g of styrene and 111 g of 90 % methacrylic acid in 250 g of water are added to 10,000 g of water, and polymerisation is initiated by the addition at 80C of a solution of 150 g of ammonium peroxodisulphate in 500 g of water. A solids concentration of 20 % by weight is reached after only 3.5 hours. The pH-value during the first polymerisation phase remains between 2.4 and 1.6. 2400 g of styrene, 2500 g Or 1,3-butadiene, 111 g of 90 /0 methacrylic acid and a solution of 100 g of ammonium peroxodisulphate in 500 g of water are then added. A solids concentration of 43.7 % by weight is reached after another 10 hours at a pH-value of 1~3. Stopping of the polymerisation reaction and working up in the same way as in Example 1 leaves a latex which, although stable, contains considerable quantities of coagulate.
In a 40 litre stainless steel reactor equipped with a crossed-arms paddle stirrer, a mi~ture of 1200 g of styrene and 1200 g of acrylonitrile, 2500 g of 1,3-butadiene and 111 g of 90 /0 methacrylic acid in 250 g Of water and 100 g of methacrylamide are polymerised at 75C in 12500 g of water with a solution of 50 g of ammonium peroxodisulphate in 500 g of water and 3~ ml of 25 oh aqueous ammonia solution. A solids concentration of 25.3 /0 by weight is reached after polymerisation rOr
4.5 hours at 75C. In the meantime, the pH-value increases from 4.6 to 5.3. A mixture of 1200 g of acrylonitrile, 1200 g of styrene and 2500 g of 1,3-butadiene is then added, followed by the introduction of a solution of Le A 18 151 ~5~
100 g of ammonium peroxodisulphate and 30 ml of 25 ~
aqueous ammonia solution in 500 g of water. A solids concentration of 43.2 /0 by weight is reached after ano~her 8 hours, and the contents of the reactor are then cooled and the polymerisation reaction stopped by the addition of 280 g of 7 /0 diethyl hydroxylamine solution. During the second polymerisation phase, the pH-value falls from 6.8 to 6.5. The latex is freed from residual monomers and adjusted to pH 9.0 with aqueous ammonia solution. After 300 g (weighed moist) of deposits have been iiltered o$f, the solids concentration amounts to 42.0 % by weight and the surface tension to 50.5 mN/m. With particle diameters between 360 and 670 nm, the latex has a wide particle size distribution.
This product may be satisfactorily mixed with large quantities of liquid phenol-formaldehyde resins.
It is therefore suitable as an elasticising agent for articles produced with phenol-formaldehyde resins, for example separator plates.
In a 40 litre stainless steel reactor equipped with a crossed-arms paddle stirrer, 12500 g of water, 1100 g of acrylonitrile, 10 g of tert.-dodecyl mercaptan and 222 g of 90 % methacrylic acid in 500 g of water are mixed and polymerised at 75C with a solution of 50 g of ammonium peroxodisulphate and 30 ml of 25 ~ aqueous ammonia solution in 500 g of water. After polymerisation for 5 hours, during which the pH-value rises from 4.0 3o to 4.5, a solids concentration of 16.3 /0 by weight is reached. A mixture of 2200 g of 1,3-butadiene, 1000 g of acrylonitrile and 40 g of tert.-dodecyl mercaptan and a solution of 50 g of ammonium peroxodisulphate and 15 ml of 25 % aqueous ammonia solution in 250 g of water Le A_18 151 ' , ~s~
are added and polymerisation is continued at pH 6.Q to 6.4 until the second polymerisation phase is terminated at a solids concentration of around 28 /0 by weight (total polymerisation time 7.5 hours). The third polymerisation phase is initiated by the addition of the same solutions as at the beginning of the second polymerisation phase.
Polymerisation is completed up to a solids concentration of 40.9 /0 by weight and, shortly beiore the final concentration is reached, is reactivated by the addition of another 20 g of ammonium peroxodisulphate in 100 g of water. In the third polymerisation phase, the pH-value remains substantially constant at 6.o. After the polymerisation reaction has been stopped by the addition of 280 g of 7 % diethyl hydroxylamine solution, the late~
is degassed in vacuo at 40C. The latex is substantially ~ree from coagulate, has a final concentration of 41.4 /0 by weight, a pH-value of 6.4 and a surface tension of 56.3 mN/m. It has a particle size distribution of from about 170 to 460 nm.
This late~ is suitable for the production of hydrophobic solver.t-resistant special papers.
Le A 18 151 :
100 g of ammonium peroxodisulphate and 30 ml of 25 ~
aqueous ammonia solution in 500 g of water. A solids concentration of 43.2 /0 by weight is reached after ano~her 8 hours, and the contents of the reactor are then cooled and the polymerisation reaction stopped by the addition of 280 g of 7 /0 diethyl hydroxylamine solution. During the second polymerisation phase, the pH-value falls from 6.8 to 6.5. The latex is freed from residual monomers and adjusted to pH 9.0 with aqueous ammonia solution. After 300 g (weighed moist) of deposits have been iiltered o$f, the solids concentration amounts to 42.0 % by weight and the surface tension to 50.5 mN/m. With particle diameters between 360 and 670 nm, the latex has a wide particle size distribution.
This product may be satisfactorily mixed with large quantities of liquid phenol-formaldehyde resins.
It is therefore suitable as an elasticising agent for articles produced with phenol-formaldehyde resins, for example separator plates.
In a 40 litre stainless steel reactor equipped with a crossed-arms paddle stirrer, 12500 g of water, 1100 g of acrylonitrile, 10 g of tert.-dodecyl mercaptan and 222 g of 90 % methacrylic acid in 500 g of water are mixed and polymerised at 75C with a solution of 50 g of ammonium peroxodisulphate and 30 ml of 25 ~ aqueous ammonia solution in 500 g of water. After polymerisation for 5 hours, during which the pH-value rises from 4.0 3o to 4.5, a solids concentration of 16.3 /0 by weight is reached. A mixture of 2200 g of 1,3-butadiene, 1000 g of acrylonitrile and 40 g of tert.-dodecyl mercaptan and a solution of 50 g of ammonium peroxodisulphate and 15 ml of 25 % aqueous ammonia solution in 250 g of water Le A_18 151 ' , ~s~
are added and polymerisation is continued at pH 6.Q to 6.4 until the second polymerisation phase is terminated at a solids concentration of around 28 /0 by weight (total polymerisation time 7.5 hours). The third polymerisation phase is initiated by the addition of the same solutions as at the beginning of the second polymerisation phase.
Polymerisation is completed up to a solids concentration of 40.9 /0 by weight and, shortly beiore the final concentration is reached, is reactivated by the addition of another 20 g of ammonium peroxodisulphate in 100 g of water. In the third polymerisation phase, the pH-value remains substantially constant at 6.o. After the polymerisation reaction has been stopped by the addition of 280 g of 7 % diethyl hydroxylamine solution, the late~
is degassed in vacuo at 40C. The latex is substantially ~ree from coagulate, has a final concentration of 41.4 /0 by weight, a pH-value of 6.4 and a surface tension of 56.3 mN/m. It has a particle size distribution of from about 170 to 460 nm.
This late~ is suitable for the production of hydrophobic solver.t-resistant special papers.
Le A 18 151 :
Claims (3)
- -l A process for the production of an emulsifier-free rubber latex from l to 6 parts by weight of (meth)-acrylic acid and 94 to 99 parts by weight of a mixture of 10 to 90 parts by weight of one or more acyclic conjugated dienes containing from 4 to 9 carbon atoms and 10 to 90 parts by weight of one or more arylvinyl monomers containing from 8 to 12 carbon atoms and/or (meth)acrylo-nitrile, the quantity of (meth)acrylonitrile amounting to at most 50 parts by weight, characterised in that a) an aqueous emulsion is prepared by adding at least part of the (meth)acrylic acid, part of the diene and other monomers to water, b) polymerisation is initiated by the addition of an aqueous solution of a peroxodisulphate, c) polymerisation is carried out in a first stage at a pH-value of from 3.5 to 7 and at a temperature above 70°C until at least 50 % of the monomers have been polymerised, d) the rest of the monomers and more aqueous peroxo-disulphate solution are added in one or more further stages, and e) polymerisation is continued at a pH-value of from 3.5 to 7 and at a temperature above 70°C until at least 50 °/0 of the monomers have been polymerised and, in the final stage, until from 85 to 100%
of the monomers have been polymerised. - 2. A process as claimed in Claim l, characterised in that up to 25 parts by weight of the non-dissociating monomers are replaced by other copolymerisable monomers.
- 3. A process as claimed in Claims l and 2, characterised in that the total quantity of the peroxodisulphate used as initiator is from 0.5 to 3.0 parts by weight, based on the total quantities of monomers.
Le A 18 151
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2830470.3 | 1978-07-11 | ||
| DE19782830470 DE2830470A1 (en) | 1978-07-11 | 1978-07-11 | METHOD FOR THE PRODUCTION OF EMULSIFIER-FREE RUBBER MATERIALS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1153140A true CA1153140A (en) | 1983-08-30 |
Family
ID=6044099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000331439A Expired CA1153140A (en) | 1978-07-11 | 1979-07-09 | Process for the production of emulsifier-free rubber latices |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0007042B2 (en) |
| JP (1) | JPS5512195A (en) |
| BR (1) | BR7904383A (en) |
| CA (1) | CA1153140A (en) |
| DE (2) | DE2830470A1 (en) |
| ES (1) | ES482362A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084505A (en) * | 1989-06-08 | 1992-01-28 | Union Oil Company Of California | Gloss latex paints and polymeric compositions for use therein |
| US5256724A (en) * | 1988-11-30 | 1993-10-26 | Rohm And Haas Company | High-gloss latex paints and polymers for use therein |
| US5326814A (en) * | 1989-01-30 | 1994-07-05 | Rohm And Haas Company | High-gloss latex paints and polymeric compositions for use therein |
| US6605663B1 (en) | 1999-06-24 | 2003-08-12 | Wacker Polymer Systems Gmbh & Co. Kg | Process for preparing polyvinyl alcohol-stabilized polymers |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3047084A1 (en) * | 1980-12-13 | 1982-07-22 | Bayer Ag, 5090 Leverkusen | CARBOXYL GROUPS CONTAINING SYNTHESIS RUBBER DISPERSIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| EP0054685B1 (en) * | 1980-12-23 | 1986-07-09 | Roche Diagnostics GmbH | Hydrophilic latex particles, process for their preparation and their use |
| DE3313922A1 (en) * | 1983-04-16 | 1984-10-25 | Hoechst Ag, 6230 Frankfurt | EMULSION AND PROTECTIVE COLLOID-FREE EMULSION POLYMERISATES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE3313923A1 (en) * | 1983-04-16 | 1984-10-18 | Hoechst Ag, 6230 Frankfurt | POLYESTER RAW MATERIAL, MOLDED BODIES MADE THEREOF, PREFERABLY A FILM, AND USE OF THE MOLDED BODIES |
| DE3939034A1 (en) * | 1989-11-25 | 1991-05-29 | Henkel Kgaa | PRODUCTION OF STABLE POLYMER DISPERSIONS BY MEANS OF AMPHOTER POLYMERS AS STABILIZERS |
| DE19545096A1 (en) * | 1995-12-04 | 1997-06-05 | Basf Ag | Process for the preparation of an aqueous polymer dispersion |
| CA2269870A1 (en) * | 1998-05-05 | 1999-11-05 | Pascale Francine Jeanne Muller | Emulsifier-free carboxylated nitrile rubber latex |
| AU2001279824A1 (en) * | 2000-09-08 | 2002-03-22 | Bayer Aktiengesellschaft | Quaternary polymers with functional amine groups |
| DE10060222A1 (en) * | 2000-12-04 | 2002-06-13 | Bayer Ag | Quaterpolymers with functional hydroxyl or epoxy groups |
| JP2007246834A (en) * | 2006-03-17 | 2007-09-27 | Asahi Kasei Chemicals Corp | Copolymer latex, paper coating composition using the same, and coated paper for offset printing use |
| EP2325237A1 (en) | 2009-11-19 | 2011-05-25 | LANXESS Deutschland GmbH | Stable fine-particle suspensions of functionalised, wholly or partially hydrated nitrile rubbers |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1011548B (en) * | 1955-01-24 | 1957-07-04 | Bayer Ag | Coating agent |
| US2913429A (en) * | 1956-03-30 | 1959-11-17 | Dow Chemical Co | Film forming synthetic latexes comprising copolymer sulfonates and method of making same |
| NL226190A (en) * | 1957-03-25 | |||
| US2868755A (en) * | 1958-01-14 | 1959-01-13 | Avrom I Medalia | Synthetic latex containing a vinyl emulsifying agent and process of preparation |
| US3306871A (en) * | 1959-09-23 | 1967-02-28 | Dow Chemical Co | Synthetic latexes comprising ar-monovinyl aromatic sulfonic acid saltstyrene-butadiene terpolymers |
| NL133104C (en) * | 1961-09-22 | |||
| US3784498A (en) * | 1972-04-21 | 1974-01-08 | Sinclair Koppers Co | Process for preparing low emulsifier synthetic latex |
| US3882070A (en) * | 1973-05-23 | 1975-05-06 | Arco Polymers Inc | Persulfate stabilized latices |
-
1978
- 1978-07-11 DE DE19782830470 patent/DE2830470A1/en not_active Withdrawn
-
1979
- 1979-06-29 EP EP79102176A patent/EP0007042B2/en not_active Expired
- 1979-06-29 DE DE7979102176T patent/DE2965188D1/en not_active Expired
- 1979-07-09 JP JP8602379A patent/JPS5512195A/en active Granted
- 1979-07-09 CA CA000331439A patent/CA1153140A/en not_active Expired
- 1979-07-10 BR BR7904383A patent/BR7904383A/en unknown
- 1979-07-10 ES ES482362A patent/ES482362A1/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256724A (en) * | 1988-11-30 | 1993-10-26 | Rohm And Haas Company | High-gloss latex paints and polymers for use therein |
| US5326814A (en) * | 1989-01-30 | 1994-07-05 | Rohm And Haas Company | High-gloss latex paints and polymeric compositions for use therein |
| US5084505A (en) * | 1989-06-08 | 1992-01-28 | Union Oil Company Of California | Gloss latex paints and polymeric compositions for use therein |
| US6605663B1 (en) | 1999-06-24 | 2003-08-12 | Wacker Polymer Systems Gmbh & Co. Kg | Process for preparing polyvinyl alcohol-stabilized polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6219764B2 (en) | 1987-05-01 |
| ES482362A1 (en) | 1980-04-01 |
| DE2830470A1 (en) | 1980-01-31 |
| BR7904383A (en) | 1980-03-25 |
| EP0007042B2 (en) | 1986-12-03 |
| JPS5512195A (en) | 1980-01-28 |
| DE2965188D1 (en) | 1983-05-19 |
| EP0007042B1 (en) | 1983-04-13 |
| EP0007042A1 (en) | 1980-01-23 |
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