CA1114976A - Process for stabilizing latex with alpha- methylstyrene-maleic anhydride adduct and stable latices produced thereby - Google Patents
Process for stabilizing latex with alpha- methylstyrene-maleic anhydride adduct and stable latices produced therebyInfo
- Publication number
- CA1114976A CA1114976A CA296,344A CA296344A CA1114976A CA 1114976 A CA1114976 A CA 1114976A CA 296344 A CA296344 A CA 296344A CA 1114976 A CA1114976 A CA 1114976A
- Authority
- CA
- Canada
- Prior art keywords
- alpha
- adduct
- maleic anhydride
- methylstyrene
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and 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
- C08F36/04—Homopolymers and 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/06—Protein or carboxylic compound containing
Abstract
Abstract of the Disclosure Latex is stabilized by the addition of small amounts of salts of maleic anhydride/alpha-methylstyrene adduct and maleic anhydride/alpha-methylstyrene dimer adduct.
me adduct salt is incorporated into the emulsifier solution used in the emulsion polymerization system.
me adduct salt is incorporated into the emulsifier solution used in the emulsion polymerization system.
Description
1~14~7~;
Background of the Invention Stabilizers or secondary emulsifiers are well known in the latex art. They are added to the emulsifier or soap solution used in the emulsion polymerization in or-der to reduce the formation of coagulum or gum. Other variables such as choice of agitation conditions can influence latex stability as well by affecting particle size and dis-tribution.
Various types of stabilizers have been used. Pro-tective colloids, exemplified by methacrylates, gelatin, pectinates, and caseinates, are frequently used in combina-tion with emulsifiers to effect micelle concentration or to prevent premature coagulation by forming a thin film at the interface between the polymer droplets and the water.
~ 15 Secondary emulsifiers, generally used at concen--~ trations between 0.04 and one weight percent based on total monomer being 100 weight percent, are divided into three groups. Anionic soaps are exemplified by alkali salts of palmitic acid, stearic acid and oleic acid. Nonionic soaps, for example, reaction products of long-chain alcohols with - ethylene oxide, are resistant to cold temperatures and chan-ges in pH. They are expensive, make coagulation difficult, and require addition of other materials such as amines for pH control and to aid in coagulation. Cationic soaps are frequently used in the latex industry and are exemplified by dodecylammonium chloride and hexadecylpyridinium chloride.
Electrolytes such as potassium chloride and so-`~ dium phosphate are also used in the soap solutions. The ; presence of an electrolyte lowers the latex viscosity and .
affects particle size. However, too much electrolyte can cream the latex or cause it to flocculate.
High molecular weight alcohols and polyhydroxy compounds can serve as stabilizers in certain cases.
One widely used dispersant stabilizer is the so-dium salt of a condensed naphthalene sulfonic acid. It is " readily soluble in water and is not appreciably affected by salts and acids although it is most effective at alkaline pH. Most latices are manufactured at a pH ranging from 9 to 12.
In using the sodium salt of a condensed naphtha-lene sulfonic acid in rubber latex manufacture, care must be taken in choosing the level at which it is used. m e quantity should be sufficient to accomplish the desired goal - of reducing prefloc or gum but not so great that it inter-feres with coagulation. In fact, it is such an effective dispersant that it causes problems in the treatment of waste water effluent from rubber manufacturing facilities.
Primary waste water treatment in these factories often consists of coagulation followed by sedimentation or flotation which processes serve to remove a substantial pro-portion of pollutants (suspended solids, chemical oxygen demand, COD, and biological oxygen demand, BOD). me sodium salt of a condensed naphthalene sulfonic acid is not affec-` 25 ted by the rubber coagulation process and remains in the supernatant spent coagulant liquor which is rejected to the waste treatment process. Unfortunately, it is also unaffec-ted by the coagulants used therein, and it resists biodegra-dation. It remains dissolved and continues through the rest of the waste treatment steps to the final discharge at least partially intact. It is a significant contributor to COD concentration, and a reduction in effluent COD is the constant goal of those working in the rubber industry.
The stabilizers of this invention, while doing an excellent job of dispersing the emulsified rubber drop-lets prior to the coagulation step, do not become part of the process effluent. Instead, they are precipitated in the rubber coagulation process with the rubber crumb.
Another stabilizer which stays with the rubber after coagulation is described ~y UOSOPatent 3,544,502 (salts of polymethylated muconic acids). However, these are added after the polymerization reaction, not as part of the reaction emulsifier solution.
Copolymers and adducts containing maleic acid ` esters and maleic anhydride are disclosed in the following references: U.SOPatent 2,912,~99 (copolymers of maleic acid esters and styrene in an organic solvent as an ingre-dient in waterproof emulsions); U~S~Patent 2,871,1~7 (salt of an adduct of maleic anhydride with SBR, NBR or another rubber as an emulsifying agent); EncycloPedia of PolYmer Science and Technology, Vol. 5, p. 822, Interscience Publ., N.Y. 1966 (styrene-maleic anhydride copolymers as a protec-tive colloid in emulsion polymerizations).
Summary of the Invention The objects of this invention are to provide: 1) a process for stabilizing latex in which the stabilizer is precipitated with the rubber crumb during the coagulation step, and 2) an emulsion composition for latex polymeriza-tions which imparts high stability to the finished polymer emulsion. Other objects and advantages will hereinafter ap-pear.
The above objects are accomplished by incorporat-ing into the emulsifier or buffer solution (used in a latex polymerization) small amounts of a salt of maleic anhydride/
alpha-methylstyrene adduct or a soap of maleic anhydride/
alpha-methylstyrene dimer adduct. There is a myriad of buf-fer solutions used in the latex industry. As a minimum they contain water and a soap. Other common ingredients are sur-factant, caustic, electrolyte and stabilizer or secondary emulsifier. ~ommonly used soaps are saturated fatty acid soaps, such as potassium stearate, and disproportionated wood rosin soaps.
Incorporation into the emulsifier solution is accomplished in the same way as is normally done in latex manufacture. The emulsifier solution is usually made by mixing all the ingredients (including stabilizer) together in an agitated tank in which the emulsifier solution is heat-: 20 ed to the proper temperature, stored, and from which it is transferred to the reactor.
The stabilizers of this invention prevent the formation of coagulum in the latex, and during the coagula-tion step by any of the common techniques (e.g. salt acid or alum) they are precipitated out of solution along with the rubber crumb. They may be utilized in any emulsion - polymerization system provided they are not substantially reactive with any member of the monomer system. For example they can be used in butadiene/styrene (SBR), acrylonitrile/
butadiene (NBR), butadiene (polybutadiene) and piperylene (polypiperylenes) monomer systems.
The adduct salts of this invention may also be utilized in NBR polymerizations as the principal emulsifier at levels of approximately 2.5 parts by weight per 100 parts by weight of monomer, replacing the sodium salt of a conden-sed naphthalene sulfonic acid in this service. meir main advantage is a reduction in plant waste water COD.
For purposes of this invention, the term "adduct"
does not mean a pure addition product but rather a mixture of oligomers of the two principal reactants, maleic anhydride and either alpha-methylstyrene or alpha-methylstyrene dimer.
The reactions hereinafter described produce a mixture which is hydrolized and neutralized to the desired product.
Alpha-methylstyrene/maleic anhydride adduct can be synthesized by mixing the two chemicals in a ratio of 1 to 3 moles maleic anhydride per mole of alpha-methylstyrene at a temperature between 150 and 210C. for 1 to 6 hours.
me reaction mixture is then stripped of volatiles under a ~- 20 vacuum. The amber product is characterized by a softening point (ASTM Method E 28-67) between 100 and 180 and by an acid number between 520 and 750.
The principal component is believed to be \
~0 CH.,;~,\C_--C~2 O//C~
l~L~
Alpha-methylstyrene dimer is a mixture of 2,4-diphenyl-4-methyl-1-pentene; 2,4-diphenyl-4-methyl-2-pentene;
and 1,1,3-trimethylphenylindane. For purposes of the present invention it is preferred that the mixture has as its major component 2,4-diphenyl-4-methyl-1-pentene and that it con-tain only minor amounts of alpha-methylstyrene trimer. One process for producing alpha-methylstyrene dimer with a high selectivity for 2,4-diphenyl-4-methyl-1-pentene is described in Belgium Patent 821,943.
Alpha-methylstyrene dimer/maleic anhydride adduct can be synthesized by thermal reaction in a manner similar to that previously described for alpha-methylstyrene. me mole ratio of maleic anhydride to alpha-methylstyrene dimer should be between 2:1 and 3:1. Temperature of the reaction may be between 100 and 195C. and reaction time may be from 1 to 6 hours. The product is stripped under a vacuum.
One of the principal components is believed to be:
~ _o CH ~ ~ di-anhydride O~c\o/c--o Hydrolysis and neutralization are carried out by treating either adduct with water and an alkali metal hydroxide. Sufficient water is used to keep the adduct salt in solution. The pH of the final adduct salt solu-tion generally varies from 9 to 12. Thus, the term salt as used herein means alkali metal salt.
.
-A more detailed description of these adduct salts and their preparation can be found in a patent application by Mario D. Zadra and James J. Tazuma entitled "Soaps of Maleic Anhydride Adducts of Alpha-Methylstyrene and Alpha-Methylstyrene Dimer" filed the same day as this application.
Preferred Embodiments of the Invention The salts of maleic anhydride/alpha-methylstyrene adduct and maleic anhydride/alpha-methylstyrene-dimer adduct will function within a pH range of 4 to 14 but they are most , stable in the higher range of 9 to 12 (most common for syn-thetic rubber latex).
The emulsifier recipe for each different latex and rubber is unique. In some cases, such as SBR, the salts of this invention may be substituted for a sodium salt of a condensed naphthalene sulfonic acid on a weight for weight basis. In other instances, for exa~ple NBR, recipe adjust-ments are necessary. For any given product some experimenta-tion is necessary to optimize the stabilizer level.
In SBR polymerizations, the adduct salts of this invention will have some stabilizing effect when utilized in amounts of from .025 to 1.0 parts by weight per 100 parts by weight of total monomer, but amounts of from .05 to 0.3 parts by weight per 100 parts by weight of total monomer are pre-ferred.
The invention will be better understood from a consideration of the following examples given for the sake of ill~stration, but with no intention of limiting the scope of the invention. Except where otherwise stated, percentages are by weight and parts are parts by weight per 100 parts .
by weight of monomer charged.
A series of five-gallon reactor batches was run at 10C. using pure monomers according to the mixed soap redox recipe shown in Table I. Various amounts of the so-dium salt of a condensed naphthalene sulfonic acid and the potassium salt of alpha-methylstyrene dimer/maleic anhydride adduct were included in the polymerization recipe to deter-mine their effect on stability.
Table I
Material Parts Water 195.0 Potassium fatty acid soap 2.25 Potassium rosin acid soap 2.25 Sodium salt of a condensed naphthalene sulfonic acid* or adduct salt Variable Tripotassium phosphate Variable Styrene 20. 5 t-Mercaptan 0.14 Water 5.0 Ferrous sulfate heptahydrate 0.004 Iron chelating agent 0. 22 Sodium formaldehyde sulfoxylate 0.044 1,3-Butadiene 75.0 Styrene 4 - 5 Paramenthane hydroperoxide 0.06 *Obtained as Tamol SN (a trademark of m e Rohm and Haas Company) The batches were polymerized to 65 percent conver-sion in approximately 10 hours. Mechanical stability of the -~ 30 latices (after steam stripping to remove residual monomers) was measured using ASTM Method D1417. Rotor speed was -` 14,000 rpm, and rotor disc diameter was 36.12 mm. Results appear in Table II.
. ~
~l o o ~ o o' 0 ~o ~ ~~ ,~ ,~ ~ ~~ o o - o o o r~~0 ~ ~ c~l~ ~ 0 u~
~1 ~ ~Lr~ ~ ~ ~ ~ 0 ~ C~
~ ~q .~l ~ ~l~ ~c`
.~l ~1 ~ ~ c~ ~ o v~
x ~0 0 ~ u~
H ~ C~cr~ ~ O
~ h ~ ~ o~
.~-rl .~ O O O O O O O O J ~ ~
E~ ~ O O O
~ , ~1 o ooo .~?~ oo?
. v~l oooo o ~
. o ~lo ?~ ?
ooo oooo ooo ~
o . ~ o ~0 ~ ~.
C~J ~ ~0 ~ ~0 C~
~ o ," , I
High shear stability data obtained on the batches containing increasing amounts of the potassium adduct salt show no general pattern but all indicate a much improved la-tex stability, comparable to tha* obtained with the sodium salt of a condensed naphthalene sulfonic acid. The data also indicate that the addition of 0.15 part of the potas-sium adduct salt to a recipe containing 0.2 part electro-lyte (tripotassium phosphate) provides a sharp improvement in latex stability. Because of material cost, it is best to use the lowest effective level of stabilizer, which from the data appears to be in the range of .05 to .15 parts.
Bottle polymerization data indicate that the potassium hydroxide salt of alpha-methylstyrene dimer/ma-leic anhydride adduct can be used as a replacement for the sodium salt of a condensed naphthalene sulfonic acid in NBR polymerizations providing certain recipe adjustments are made. If the dimer adduct salt is used at a level of
Background of the Invention Stabilizers or secondary emulsifiers are well known in the latex art. They are added to the emulsifier or soap solution used in the emulsion polymerization in or-der to reduce the formation of coagulum or gum. Other variables such as choice of agitation conditions can influence latex stability as well by affecting particle size and dis-tribution.
Various types of stabilizers have been used. Pro-tective colloids, exemplified by methacrylates, gelatin, pectinates, and caseinates, are frequently used in combina-tion with emulsifiers to effect micelle concentration or to prevent premature coagulation by forming a thin film at the interface between the polymer droplets and the water.
~ 15 Secondary emulsifiers, generally used at concen--~ trations between 0.04 and one weight percent based on total monomer being 100 weight percent, are divided into three groups. Anionic soaps are exemplified by alkali salts of palmitic acid, stearic acid and oleic acid. Nonionic soaps, for example, reaction products of long-chain alcohols with - ethylene oxide, are resistant to cold temperatures and chan-ges in pH. They are expensive, make coagulation difficult, and require addition of other materials such as amines for pH control and to aid in coagulation. Cationic soaps are frequently used in the latex industry and are exemplified by dodecylammonium chloride and hexadecylpyridinium chloride.
Electrolytes such as potassium chloride and so-`~ dium phosphate are also used in the soap solutions. The ; presence of an electrolyte lowers the latex viscosity and .
affects particle size. However, too much electrolyte can cream the latex or cause it to flocculate.
High molecular weight alcohols and polyhydroxy compounds can serve as stabilizers in certain cases.
One widely used dispersant stabilizer is the so-dium salt of a condensed naphthalene sulfonic acid. It is " readily soluble in water and is not appreciably affected by salts and acids although it is most effective at alkaline pH. Most latices are manufactured at a pH ranging from 9 to 12.
In using the sodium salt of a condensed naphtha-lene sulfonic acid in rubber latex manufacture, care must be taken in choosing the level at which it is used. m e quantity should be sufficient to accomplish the desired goal - of reducing prefloc or gum but not so great that it inter-feres with coagulation. In fact, it is such an effective dispersant that it causes problems in the treatment of waste water effluent from rubber manufacturing facilities.
Primary waste water treatment in these factories often consists of coagulation followed by sedimentation or flotation which processes serve to remove a substantial pro-portion of pollutants (suspended solids, chemical oxygen demand, COD, and biological oxygen demand, BOD). me sodium salt of a condensed naphthalene sulfonic acid is not affec-` 25 ted by the rubber coagulation process and remains in the supernatant spent coagulant liquor which is rejected to the waste treatment process. Unfortunately, it is also unaffec-ted by the coagulants used therein, and it resists biodegra-dation. It remains dissolved and continues through the rest of the waste treatment steps to the final discharge at least partially intact. It is a significant contributor to COD concentration, and a reduction in effluent COD is the constant goal of those working in the rubber industry.
The stabilizers of this invention, while doing an excellent job of dispersing the emulsified rubber drop-lets prior to the coagulation step, do not become part of the process effluent. Instead, they are precipitated in the rubber coagulation process with the rubber crumb.
Another stabilizer which stays with the rubber after coagulation is described ~y UOSOPatent 3,544,502 (salts of polymethylated muconic acids). However, these are added after the polymerization reaction, not as part of the reaction emulsifier solution.
Copolymers and adducts containing maleic acid ` esters and maleic anhydride are disclosed in the following references: U.SOPatent 2,912,~99 (copolymers of maleic acid esters and styrene in an organic solvent as an ingre-dient in waterproof emulsions); U~S~Patent 2,871,1~7 (salt of an adduct of maleic anhydride with SBR, NBR or another rubber as an emulsifying agent); EncycloPedia of PolYmer Science and Technology, Vol. 5, p. 822, Interscience Publ., N.Y. 1966 (styrene-maleic anhydride copolymers as a protec-tive colloid in emulsion polymerizations).
Summary of the Invention The objects of this invention are to provide: 1) a process for stabilizing latex in which the stabilizer is precipitated with the rubber crumb during the coagulation step, and 2) an emulsion composition for latex polymeriza-tions which imparts high stability to the finished polymer emulsion. Other objects and advantages will hereinafter ap-pear.
The above objects are accomplished by incorporat-ing into the emulsifier or buffer solution (used in a latex polymerization) small amounts of a salt of maleic anhydride/
alpha-methylstyrene adduct or a soap of maleic anhydride/
alpha-methylstyrene dimer adduct. There is a myriad of buf-fer solutions used in the latex industry. As a minimum they contain water and a soap. Other common ingredients are sur-factant, caustic, electrolyte and stabilizer or secondary emulsifier. ~ommonly used soaps are saturated fatty acid soaps, such as potassium stearate, and disproportionated wood rosin soaps.
Incorporation into the emulsifier solution is accomplished in the same way as is normally done in latex manufacture. The emulsifier solution is usually made by mixing all the ingredients (including stabilizer) together in an agitated tank in which the emulsifier solution is heat-: 20 ed to the proper temperature, stored, and from which it is transferred to the reactor.
The stabilizers of this invention prevent the formation of coagulum in the latex, and during the coagula-tion step by any of the common techniques (e.g. salt acid or alum) they are precipitated out of solution along with the rubber crumb. They may be utilized in any emulsion - polymerization system provided they are not substantially reactive with any member of the monomer system. For example they can be used in butadiene/styrene (SBR), acrylonitrile/
butadiene (NBR), butadiene (polybutadiene) and piperylene (polypiperylenes) monomer systems.
The adduct salts of this invention may also be utilized in NBR polymerizations as the principal emulsifier at levels of approximately 2.5 parts by weight per 100 parts by weight of monomer, replacing the sodium salt of a conden-sed naphthalene sulfonic acid in this service. meir main advantage is a reduction in plant waste water COD.
For purposes of this invention, the term "adduct"
does not mean a pure addition product but rather a mixture of oligomers of the two principal reactants, maleic anhydride and either alpha-methylstyrene or alpha-methylstyrene dimer.
The reactions hereinafter described produce a mixture which is hydrolized and neutralized to the desired product.
Alpha-methylstyrene/maleic anhydride adduct can be synthesized by mixing the two chemicals in a ratio of 1 to 3 moles maleic anhydride per mole of alpha-methylstyrene at a temperature between 150 and 210C. for 1 to 6 hours.
me reaction mixture is then stripped of volatiles under a ~- 20 vacuum. The amber product is characterized by a softening point (ASTM Method E 28-67) between 100 and 180 and by an acid number between 520 and 750.
The principal component is believed to be \
~0 CH.,;~,\C_--C~2 O//C~
l~L~
Alpha-methylstyrene dimer is a mixture of 2,4-diphenyl-4-methyl-1-pentene; 2,4-diphenyl-4-methyl-2-pentene;
and 1,1,3-trimethylphenylindane. For purposes of the present invention it is preferred that the mixture has as its major component 2,4-diphenyl-4-methyl-1-pentene and that it con-tain only minor amounts of alpha-methylstyrene trimer. One process for producing alpha-methylstyrene dimer with a high selectivity for 2,4-diphenyl-4-methyl-1-pentene is described in Belgium Patent 821,943.
Alpha-methylstyrene dimer/maleic anhydride adduct can be synthesized by thermal reaction in a manner similar to that previously described for alpha-methylstyrene. me mole ratio of maleic anhydride to alpha-methylstyrene dimer should be between 2:1 and 3:1. Temperature of the reaction may be between 100 and 195C. and reaction time may be from 1 to 6 hours. The product is stripped under a vacuum.
One of the principal components is believed to be:
~ _o CH ~ ~ di-anhydride O~c\o/c--o Hydrolysis and neutralization are carried out by treating either adduct with water and an alkali metal hydroxide. Sufficient water is used to keep the adduct salt in solution. The pH of the final adduct salt solu-tion generally varies from 9 to 12. Thus, the term salt as used herein means alkali metal salt.
.
-A more detailed description of these adduct salts and their preparation can be found in a patent application by Mario D. Zadra and James J. Tazuma entitled "Soaps of Maleic Anhydride Adducts of Alpha-Methylstyrene and Alpha-Methylstyrene Dimer" filed the same day as this application.
Preferred Embodiments of the Invention The salts of maleic anhydride/alpha-methylstyrene adduct and maleic anhydride/alpha-methylstyrene-dimer adduct will function within a pH range of 4 to 14 but they are most , stable in the higher range of 9 to 12 (most common for syn-thetic rubber latex).
The emulsifier recipe for each different latex and rubber is unique. In some cases, such as SBR, the salts of this invention may be substituted for a sodium salt of a condensed naphthalene sulfonic acid on a weight for weight basis. In other instances, for exa~ple NBR, recipe adjust-ments are necessary. For any given product some experimenta-tion is necessary to optimize the stabilizer level.
In SBR polymerizations, the adduct salts of this invention will have some stabilizing effect when utilized in amounts of from .025 to 1.0 parts by weight per 100 parts by weight of total monomer, but amounts of from .05 to 0.3 parts by weight per 100 parts by weight of total monomer are pre-ferred.
The invention will be better understood from a consideration of the following examples given for the sake of ill~stration, but with no intention of limiting the scope of the invention. Except where otherwise stated, percentages are by weight and parts are parts by weight per 100 parts .
by weight of monomer charged.
A series of five-gallon reactor batches was run at 10C. using pure monomers according to the mixed soap redox recipe shown in Table I. Various amounts of the so-dium salt of a condensed naphthalene sulfonic acid and the potassium salt of alpha-methylstyrene dimer/maleic anhydride adduct were included in the polymerization recipe to deter-mine their effect on stability.
Table I
Material Parts Water 195.0 Potassium fatty acid soap 2.25 Potassium rosin acid soap 2.25 Sodium salt of a condensed naphthalene sulfonic acid* or adduct salt Variable Tripotassium phosphate Variable Styrene 20. 5 t-Mercaptan 0.14 Water 5.0 Ferrous sulfate heptahydrate 0.004 Iron chelating agent 0. 22 Sodium formaldehyde sulfoxylate 0.044 1,3-Butadiene 75.0 Styrene 4 - 5 Paramenthane hydroperoxide 0.06 *Obtained as Tamol SN (a trademark of m e Rohm and Haas Company) The batches were polymerized to 65 percent conver-sion in approximately 10 hours. Mechanical stability of the -~ 30 latices (after steam stripping to remove residual monomers) was measured using ASTM Method D1417. Rotor speed was -` 14,000 rpm, and rotor disc diameter was 36.12 mm. Results appear in Table II.
. ~
~l o o ~ o o' 0 ~o ~ ~~ ,~ ,~ ~ ~~ o o - o o o r~~0 ~ ~ c~l~ ~ 0 u~
~1 ~ ~Lr~ ~ ~ ~ ~ 0 ~ C~
~ ~q .~l ~ ~l~ ~c`
.~l ~1 ~ ~ c~ ~ o v~
x ~0 0 ~ u~
H ~ C~cr~ ~ O
~ h ~ ~ o~
.~-rl .~ O O O O O O O O J ~ ~
E~ ~ O O O
~ , ~1 o ooo .~?~ oo?
. v~l oooo o ~
. o ~lo ?~ ?
ooo oooo ooo ~
o . ~ o ~0 ~ ~.
C~J ~ ~0 ~ ~0 C~
~ o ," , I
High shear stability data obtained on the batches containing increasing amounts of the potassium adduct salt show no general pattern but all indicate a much improved la-tex stability, comparable to tha* obtained with the sodium salt of a condensed naphthalene sulfonic acid. The data also indicate that the addition of 0.15 part of the potas-sium adduct salt to a recipe containing 0.2 part electro-lyte (tripotassium phosphate) provides a sharp improvement in latex stability. Because of material cost, it is best to use the lowest effective level of stabilizer, which from the data appears to be in the range of .05 to .15 parts.
Bottle polymerization data indicate that the potassium hydroxide salt of alpha-methylstyrene dimer/ma-leic anhydride adduct can be used as a replacement for the sodium salt of a condensed naphthalene sulfonic acid in NBR polymerizations providing certain recipe adjustments are made. If the dimer adduct salt is used at a level of
2.5 parts, experiments have shown that satisfactory latex - stability is obtained if the level of a secondary surfac-tant, a linear alkyl sulfonate, is increased from about 0.2 parts to between about 0.8 and 2.0 parts.
While certain representative embodiments and de-tails have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art -~ 25 that various changes and modifications may be made therein without departing from -the spirit or scope of the invention.
. .
.~
.
.
While certain representative embodiments and de-tails have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art -~ 25 that various changes and modifications may be made therein without departing from -the spirit or scope of the invention.
. .
.~
.
.
Claims (7)
1. In a process for synthesizing an emulsion polymer, the improvement which comprises incorporating a salt selected from the group consisting of salts of alpha-methylstyrene/maleic anhydride adduct and salts of alpha-methylstyrene dimer/maleic anhydride adduct into the emul-sifier solution.
2. The process as recited in Claim 1 wherein the emulsion polymer is NBR and the adduct salt is utilized at a level of approximately 2.5 parts per 100 parts of mono-mer.
3. The process as recited in Claim 1 wherein the emulsion polymer is styrene-butadiene rubber and the adduct salt is utilized at a level of .025 to 1.0 parts per 100 parts of monomer.
4. The stable aqueous synthetic rubber latex synthesized by the process recited in Claim 3.
5. The process as recited in Claim 3 wherein the adduct salt is utilized at a level of from .05 to .3 parts per 100 parts of monomer.
6. The process as recited in Claim 5 which fur-ther comprises incorporating an electrolyte into the emul-sifier solution.
7. The process of Claim 6 in which the electro-lyte is tripotassium phosphate at a concentration of .2 to .6 parts per 100 parts of monomer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/790,113 US4110293A (en) | 1977-04-22 | 1977-04-22 | Process for stabilizing latex and stable latices produced thereby |
| US790,113 | 1977-04-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1114976A true CA1114976A (en) | 1981-12-22 |
Family
ID=25149679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA296,344A Expired CA1114976A (en) | 1977-04-22 | 1978-02-06 | Process for stabilizing latex with alpha- methylstyrene-maleic anhydride adduct and stable latices produced thereby |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4110293A (en) |
| JP (1) | JPS6049202B2 (en) |
| AU (1) | AU3492278A (en) |
| BR (1) | BR7802380A (en) |
| CA (1) | CA1114976A (en) |
| DE (1) | DE2812349C2 (en) |
| FR (1) | FR2387998A1 (en) |
| GB (1) | GB1566793A (en) |
| ZA (1) | ZA781602B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236242A (en) * | 1988-07-27 | 1990-02-06 | Katetsukusu:Kk | Sbr latex corresponding to silicate ion and sbr latex material |
| US6525116B2 (en) | 1999-01-26 | 2003-02-25 | National Gypsum Properties Llc | Gypsum composition with ionic styrene butadiene latex additive |
| CA2763509C (en) * | 2009-05-28 | 2018-01-16 | Dow Global Technologies Llc | Modified geopolymer compositions, processes and uses |
| US20110094320A1 (en) * | 2009-10-26 | 2011-04-28 | Liang Hong | Method for evaluating de-agglomeration/coagulation stability of agglomerates materials |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2465888A (en) * | 1946-10-18 | 1949-03-29 | Ray V Lawrence | Butadiene emulsion polymerization in the presence of levopimaric acid-maleic anhydride addition product esters |
| US2912399A (en) * | 1953-08-11 | 1959-11-10 | Bayer Ag | Process for preparing aqueous emulsions |
| US2871137A (en) * | 1955-06-13 | 1959-01-27 | Exxon Research Engineering Co | Method for preparing emulsifying agents and emulsions prepared therefrom |
| US3258437A (en) * | 1961-06-05 | 1966-06-28 | Pittsburgh Plate Glass Co | Polymerization of dienes in the presence of an amine or ammonia salt and product thereof |
| US3544502A (en) * | 1968-05-23 | 1970-12-01 | Sun Oil Co | Latex stabilized with salts of polymethylated muconic acids |
| US4017560A (en) * | 1974-09-30 | 1977-04-12 | The Goodyear Tire & Rubber Company | Aqueous emulsion latex derived rubbery copolymer |
-
1977
- 1977-04-22 US US05/790,113 patent/US4110293A/en not_active Expired - Lifetime
-
1978
- 1978-02-06 CA CA296,344A patent/CA1114976A/en not_active Expired
- 1978-03-15 GB GB10237/78A patent/GB1566793A/en not_active Expired
- 1978-03-20 ZA ZA00781602A patent/ZA781602B/en unknown
- 1978-03-21 DE DE2812349A patent/DE2812349C2/en not_active Expired
- 1978-04-10 AU AU34922/78A patent/AU3492278A/en active Pending
- 1978-04-18 BR BR7802380A patent/BR7802380A/en unknown
- 1978-04-20 JP JP53047161A patent/JPS6049202B2/en not_active Expired
- 1978-04-20 FR FR7811666A patent/FR2387998A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| ZA781602B (en) | 1979-03-28 |
| DE2812349C2 (en) | 1986-11-06 |
| GB1566793A (en) | 1980-05-08 |
| DE2812349A1 (en) | 1978-10-26 |
| AU3492278A (en) | 1979-10-18 |
| JPS53133284A (en) | 1978-11-20 |
| BR7802380A (en) | 1978-12-19 |
| FR2387998B1 (en) | 1980-10-31 |
| US4110293A (en) | 1978-08-29 |
| FR2387998A1 (en) | 1978-11-17 |
| JPS6049202B2 (en) | 1985-10-31 |
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