CA2009182A1 - Aqueous synthetic resin dispersions - Google Patents
Aqueous synthetic resin dispersionsInfo
- Publication number
- CA2009182A1 CA2009182A1 CA002009182A CA2009182A CA2009182A1 CA 2009182 A1 CA2009182 A1 CA 2009182A1 CA 002009182 A CA002009182 A CA 002009182A CA 2009182 A CA2009182 A CA 2009182A CA 2009182 A1 CA2009182 A1 CA 2009182A1
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- CA
- Canada
- Prior art keywords
- weight
- monomers
- monomer
- feed
- polymerization
- 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.)
- Abandoned
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
- 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
- C08F236/12—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 with nitriles
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/08—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of nitriles
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure: Aqueous synthetic resin dis-persions are obtainable by copolymerizing A) from 70 to 97.5 parts by weight of a monomer mixture containing a) from 40 to 75% by weight of butadiene (monomer I), b) from 25 to 60% by weight of acrylonitrile (monomer II), c) from 0 to 25% by weight of styrene (monomer III), d) from 0 to 10% by weight of one or more amides of .alpha.,.beta.monoethylenically unsaturated monocarboxylic acids of 3 to 5 carbon atom (monomers IV) and e) from 0 to 10% by weight of other copolymerizable monomers (monomers V) and B) from 2.5 to 30 parts by weight of one or more co-polymerizable monovinyl compounds (monomers VI) in aqueous emulsion at from 30 to 70°C by a method in which not less than 50% by weight of the monomer mixture A is prepolymerized to a conversion of not less than 80%, and the polymerization is then continued with the addi-tion of the remaining monomers A and the monomer B.
These dispersions are suitable as binders for protective coats on leather.
These dispersions are suitable as binders for protective coats on leather.
Description
91~:~
- O.Z. 0050/40587 A~ueous synthetic resin disper~ions The present invention relates to aqueou~ syn-thetic re~in dispersions, obtainable by copolymerizing A) from 70 to 97.5 parts by weight of a monomer mixture S containing a) from 40 to 75% by weight of butadiene (monomer I), b) from 25 to 60~ by weight of acrylonitrile (monomer II), c) from 0 to 25~ by weight of styrene (monomer III), d) from 0 to 10% by weight of one or more amides of monoethylenically unsaturated monocarboxylic acids of 3 to 5 carbon atom~ (monomers IY) and e) from 0 to 10% by weight of other copolymerizable lS monomer~ (monomers V) and B) from 2.5 to 30 parts by weight of one or more co-polymerizable monovinyl compounds tmonomers VI) at from 30 to 70C in aqueous emulsion qo that not less than 50% by weight of the monomer mixture A is prepoly-merized to a conversion of not less than 80~, and then continuing the polymerization with the addition of the remaining monomers A and the monomers B.
The pressnt invention furthermore relate~ to a process for the preparation of these dispersion~ and the u3e of these di-Qpersions as binder~ for protective coats on leather.
EP-B 29170 di~closes carboxylated synthetic rubbor dispersion~ which, after the addition of oxides and/or hydro~ide of divalent metal~, are recommended a~
binders for protective coats on leather, in order to Lmpart to these protective coats both good dry flexing resistance and good wet flexing re i3~ance. ~owever, the performance characteri~tics of these binder3 were not completely sati~factory with respect to the -~et flexing resistance of the resulting leather protective coats.
Moreover, they do not have completely 3atisfactory low :~ .
~.
.
- O.Z. 0050/40587 A~ueous synthetic resin disper~ions The present invention relates to aqueou~ syn-thetic re~in dispersions, obtainable by copolymerizing A) from 70 to 97.5 parts by weight of a monomer mixture S containing a) from 40 to 75% by weight of butadiene (monomer I), b) from 25 to 60~ by weight of acrylonitrile (monomer II), c) from 0 to 25~ by weight of styrene (monomer III), d) from 0 to 10% by weight of one or more amides of monoethylenically unsaturated monocarboxylic acids of 3 to 5 carbon atom~ (monomers IY) and e) from 0 to 10% by weight of other copolymerizable lS monomer~ (monomers V) and B) from 2.5 to 30 parts by weight of one or more co-polymerizable monovinyl compounds tmonomers VI) at from 30 to 70C in aqueous emulsion qo that not less than 50% by weight of the monomer mixture A is prepoly-merized to a conversion of not less than 80~, and then continuing the polymerization with the addition of the remaining monomers A and the monomers B.
The pressnt invention furthermore relate~ to a process for the preparation of these dispersion~ and the u3e of these di-Qpersions as binder~ for protective coats on leather.
EP-B 29170 di~closes carboxylated synthetic rubbor dispersion~ which, after the addition of oxides and/or hydro~ide of divalent metal~, are recommended a~
binders for protective coats on leather, in order to Lmpart to these protective coats both good dry flexing resistance and good wet flexing re i3~ance. ~owever, the performance characteri~tics of these binder3 were not completely sati~factory with respect to the -~et flexing resistance of the resulting leather protective coats.
Moreover, they do not have completely 3atisfactory low :~ .
~.
.
- 2 - O.Z. 0050/40587 temperature breaking streng~h.~ O ~ 9~8Z
It is an object of the present invention to over-come the disadvantages described by means of synthetic resin dispersions which are particularly ~uitable as binders for protective coats on leather.
We have found that this object i~ achieved by the synthetic resin dispersions as defined at the outset.
The amides of acrylic acid or methacrylic acid are advantageously copolymerized as monomers IV, and particularly suitable monomer~ V are the acrylates and methacrylates of C1-C8~alkanols, methacrylonitrile, N-alkyl derivatives of acrylamide and methacrylamide, which derivativeY carry lower alkyl group~, and vinylaromatic compound~, ~uch as styrene. Preferred esters of acrylic acid and of methacrylic acid are methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate and 2-ethylhexyl acrylate, while N-methylmethacrylamide is a preferred copolymer from among the said N-alkyl deriva-tives. Particularly suitable monomer mixtures A have the following composition:
from 40 to 65~ by weight of butadiene, from 25 to 35% by weight of acrylonitrile, from 5 to 50% by weight of styrene, from 2 to 7% by weight of acrylamide and/or methacryl-amide and from 0 to 10% by weight of monomer V.
Particularly suitable monomers VI are acrylic acid, methacrylic acid and the monomers V. Styrene and methyl methacrylate are particularly advantageou~ly copolymerized a~ monomers VI. Advantageously, from 3 to 22% by weight, based on the monomer~ A, of monomers B are incorporated.
The novel ~ynthetic resin di~persion~ are advan-tageou~ly prepared in a pressure vessel by polymeri~ation of the particular monomer~ in an aqueous medium under the known conditions of emul~ion polymerization in the presenc2 of water-~oluble free radical initiator~ and :
.
~ 3 ~ 9~. z . 0050/40587 emulsifiers and in the presence or absence of regulators, buffer substances and further assistants, by prepolymer-izing not less than 50% by weight of monomer mixture A to a conversion of not less than 80% and then continuing the S polymerization with the addition of the remaining monom-er~ A and the monomers B. The polymerization temperature is from 30 to 70C, preferably from 45 to 65C.
The prepolymerization, which in accordance with the definition may include the total amount of the monomers A, may be carried out either a~ a batchwise pro-ces or a~ a feed process.~ The feed process in which an initially taken part of the polymerization mixture is heated to the polymerization temperature and the remain-der i~ then fed in continuou~ly while maintaining the lS polymerization temperature is preferred. In this proced-ure, the monomers A can be introduced in pure or emul-sified form or a~ an aqueous ~olution. The monomer~ A
are preferably fed in as an aqueous emulsion. The initially taken material may be only water or may inc~ude other ~ub~tance~ taking part in the polymerization, such a~ monomers A, initiators or emulsifiers. The initially taken material particularly advantageously contains from 25 to 35% by weight of the amount of water used for the total emul~ion polymerization, from 5 to 10% by weight of the total amount of monomers A, the total amount of initiators and a proportion of the total amount of emul-sifier~ which corresponds to the initially taken amount of monomers A.
A~ a batchwise proces~, the prepolymerization take~, a~ a rule, from 2 to 10 hours, depending on the amount of monomer~ A used. In the feed process, the continuou~ feed of the polymer~ A to be prepolymerized usually take~ the same tLme.
Continued polymerization with the addition of the remaining monomer~ A and the monomer~ B is carried out immediately after the prepolymerization, and once again the monomers may be added in pure or emul~ified form or ~ 9~8~ o.z. 0050/40587 as an aqueous solution, all at once or continuously. The remaining monomers A and the monomers B may be added either at separate points or via a common feed vessel and in any order. While the feed rate of monomers B is of minor importance, the feed of the remaining monomers A
should not be slower than in the case of prepolymeriza-tion by the feed process. In a preferred embodiment, the feed of monomers B begins when 80% of the total amount of monomers A have already been fed into the initially taken mixture during prepolymerization by the feed process, the addition of the monomers B being carried out synch-ronously with the continuous addition of the remaining monomers A. After the end of the monomer feed, poly-merization i~ advantageously continued for a few hours.
Examples of suitable water-soluble polymerization initiator~ ar~ inorganic peroxo compounds, such as hydro-gan peroxide, sodium peroxydisulfate, pota~ium peroxy-disulfate or ammonium peroxydisulfate, and organic perox-ides or hydroperoxides, such as tert-butyl hydroperoxide or tert-butyl perbenzoate. The amount of initiator used is from 0.05 to 0.6% by weight, based on the total amount of monomers used. The organic peroxo compounds are preferably employed in combination with suitable reducing agents. Examples of such reducing agents are sulfur di-oxide, thio~ulfate, dithionite, hydrazine sulfate,glucose, a~corbic acid and sodium hydroxymethane-sulfinata.
Emulsifiers which have proven particularly useful are alkali metal ~alts of higher fatty alcohol sulfate~, ~uch a~ Na n-laurylsulfate, ethoxylated alkylphenols (degree of ethoxylation from 3 to 30, Ca-C10-alkyl radi-cal) and ethoxylated fatty alcohol~ (degree of ethoxyla-tion from S to 50, C~--C25-alkyl radical). Emul~ifiex mix-tures are preferably used. In some ca~es, the addition of buffer sub3tances, such a ~etr~sodium diphosphate, proves ad~antageous for bringing the pH of the polymer-ization medium to 2 10. The emulsion polymerization is z - s - O.Z. 0050/40587 preferably carried out at a pH of from 4 to 9. Chain transfer agents, such as tetrabromomethane, tetrabromo-ethane or higher alkyl mercaptans, such as tert-dodecyl mercaptan, may also be used in the polymerization. They are particularly advantageously added when the emulsion polymerization is carried out at fairly high tempera-tures. llhe solids content of the novel dispersions is of minor importance. It is advantageou~ly from 30 to 60~ by weight. The novel aqueous synthetic resin dispersions even alone are more suitable as binders for the produc-tion of protective coats having high low temperature breaking strength and good dry and wet flexing re~istance than the carboxylated synthetic rubber dispersion~ of EP-B 29170 after the addition of oxides and/or hydroxides of divalent metals. They can be used on both full-grained or buffed leather and on split leather fiber materials.
They are usually used with a solids content of from 15 to 40% by weight.
To meet fashion requirements, colored leather protsctive coats are generally applied. For this pur-pose, aqueous pigment formulations, which usually con-tain, a~ e3sential component~, water, finely divided inorganic or organic pigment~ (eg. iron oxide, titanium dioxide, azo pigments, phthalocyanine~ or carbon black), di~persant~ or, if required, thickeners, ~uch as casein, thermoplastic or nonthermopla~ic binder and fur~her assistant3~ such a~ preservative~, are generally stirred into the synthetic re~in dispersions serving as binders.
The colored leather protective formulations thus obtainabls are applied to the leather by curtain coating, knife coating, ~preading, spraying or brushing or by the plush proces~. In general, a base protective coat is ir~t applied, ironing i~ carried out and a top coat of the ~ame composition is then applied. After drying of the top coat i8 complete, nitrocellulose or other cellu-lose esters are among the suitable binder-containing ~easons ~or imparting the desired glo~s or physical - 6 - O.Z. 0050/40587 fastness properties to the protective coat.
EXAMPLES
Preparation of various synthetic resin dispersions Bl ~o A mixture of 12 g of sodium peroxydisulfate, 1.6 kg of water and 9.1% of feed 1 was initially taken in a pressure vessel and heated to the polymerization tempera-ture of 55C in the course of 30 minute~. Thereafter, the remaining amount of feed 1 was introduced in the course of 6 hours via a feed vecsel 1 while maintaining the polymerization temperature, the said feed 1 being supplemented duriny the final two hour~ by feed 2 intro-duced via a feed vessel 2. After the end of the monomer feed, polymerization was continued for a further 8.5 hours. The ~olids content of the resulting dispersion was 38.6% by weight.
Feed 1:
It is an object of the present invention to over-come the disadvantages described by means of synthetic resin dispersions which are particularly ~uitable as binders for protective coats on leather.
We have found that this object i~ achieved by the synthetic resin dispersions as defined at the outset.
The amides of acrylic acid or methacrylic acid are advantageously copolymerized as monomers IV, and particularly suitable monomer~ V are the acrylates and methacrylates of C1-C8~alkanols, methacrylonitrile, N-alkyl derivatives of acrylamide and methacrylamide, which derivativeY carry lower alkyl group~, and vinylaromatic compound~, ~uch as styrene. Preferred esters of acrylic acid and of methacrylic acid are methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate and 2-ethylhexyl acrylate, while N-methylmethacrylamide is a preferred copolymer from among the said N-alkyl deriva-tives. Particularly suitable monomer mixtures A have the following composition:
from 40 to 65~ by weight of butadiene, from 25 to 35% by weight of acrylonitrile, from 5 to 50% by weight of styrene, from 2 to 7% by weight of acrylamide and/or methacryl-amide and from 0 to 10% by weight of monomer V.
Particularly suitable monomers VI are acrylic acid, methacrylic acid and the monomers V. Styrene and methyl methacrylate are particularly advantageou~ly copolymerized a~ monomers VI. Advantageously, from 3 to 22% by weight, based on the monomer~ A, of monomers B are incorporated.
The novel ~ynthetic resin di~persion~ are advan-tageou~ly prepared in a pressure vessel by polymeri~ation of the particular monomer~ in an aqueous medium under the known conditions of emul~ion polymerization in the presenc2 of water-~oluble free radical initiator~ and :
.
~ 3 ~ 9~. z . 0050/40587 emulsifiers and in the presence or absence of regulators, buffer substances and further assistants, by prepolymer-izing not less than 50% by weight of monomer mixture A to a conversion of not less than 80% and then continuing the S polymerization with the addition of the remaining monom-er~ A and the monomers B. The polymerization temperature is from 30 to 70C, preferably from 45 to 65C.
The prepolymerization, which in accordance with the definition may include the total amount of the monomers A, may be carried out either a~ a batchwise pro-ces or a~ a feed process.~ The feed process in which an initially taken part of the polymerization mixture is heated to the polymerization temperature and the remain-der i~ then fed in continuou~ly while maintaining the lS polymerization temperature is preferred. In this proced-ure, the monomers A can be introduced in pure or emul-sified form or a~ an aqueous ~olution. The monomer~ A
are preferably fed in as an aqueous emulsion. The initially taken material may be only water or may inc~ude other ~ub~tance~ taking part in the polymerization, such a~ monomers A, initiators or emulsifiers. The initially taken material particularly advantageously contains from 25 to 35% by weight of the amount of water used for the total emul~ion polymerization, from 5 to 10% by weight of the total amount of monomers A, the total amount of initiators and a proportion of the total amount of emul-sifier~ which corresponds to the initially taken amount of monomers A.
A~ a batchwise proces~, the prepolymerization take~, a~ a rule, from 2 to 10 hours, depending on the amount of monomer~ A used. In the feed process, the continuou~ feed of the polymer~ A to be prepolymerized usually take~ the same tLme.
Continued polymerization with the addition of the remaining monomer~ A and the monomer~ B is carried out immediately after the prepolymerization, and once again the monomers may be added in pure or emul~ified form or ~ 9~8~ o.z. 0050/40587 as an aqueous solution, all at once or continuously. The remaining monomers A and the monomers B may be added either at separate points or via a common feed vessel and in any order. While the feed rate of monomers B is of minor importance, the feed of the remaining monomers A
should not be slower than in the case of prepolymeriza-tion by the feed process. In a preferred embodiment, the feed of monomers B begins when 80% of the total amount of monomers A have already been fed into the initially taken mixture during prepolymerization by the feed process, the addition of the monomers B being carried out synch-ronously with the continuous addition of the remaining monomers A. After the end of the monomer feed, poly-merization i~ advantageously continued for a few hours.
Examples of suitable water-soluble polymerization initiator~ ar~ inorganic peroxo compounds, such as hydro-gan peroxide, sodium peroxydisulfate, pota~ium peroxy-disulfate or ammonium peroxydisulfate, and organic perox-ides or hydroperoxides, such as tert-butyl hydroperoxide or tert-butyl perbenzoate. The amount of initiator used is from 0.05 to 0.6% by weight, based on the total amount of monomers used. The organic peroxo compounds are preferably employed in combination with suitable reducing agents. Examples of such reducing agents are sulfur di-oxide, thio~ulfate, dithionite, hydrazine sulfate,glucose, a~corbic acid and sodium hydroxymethane-sulfinata.
Emulsifiers which have proven particularly useful are alkali metal ~alts of higher fatty alcohol sulfate~, ~uch a~ Na n-laurylsulfate, ethoxylated alkylphenols (degree of ethoxylation from 3 to 30, Ca-C10-alkyl radi-cal) and ethoxylated fatty alcohol~ (degree of ethoxyla-tion from S to 50, C~--C25-alkyl radical). Emul~ifiex mix-tures are preferably used. In some ca~es, the addition of buffer sub3tances, such a ~etr~sodium diphosphate, proves ad~antageous for bringing the pH of the polymer-ization medium to 2 10. The emulsion polymerization is z - s - O.Z. 0050/40587 preferably carried out at a pH of from 4 to 9. Chain transfer agents, such as tetrabromomethane, tetrabromo-ethane or higher alkyl mercaptans, such as tert-dodecyl mercaptan, may also be used in the polymerization. They are particularly advantageously added when the emulsion polymerization is carried out at fairly high tempera-tures. llhe solids content of the novel dispersions is of minor importance. It is advantageou~ly from 30 to 60~ by weight. The novel aqueous synthetic resin dispersions even alone are more suitable as binders for the produc-tion of protective coats having high low temperature breaking strength and good dry and wet flexing re~istance than the carboxylated synthetic rubber dispersion~ of EP-B 29170 after the addition of oxides and/or hydroxides of divalent metals. They can be used on both full-grained or buffed leather and on split leather fiber materials.
They are usually used with a solids content of from 15 to 40% by weight.
To meet fashion requirements, colored leather protsctive coats are generally applied. For this pur-pose, aqueous pigment formulations, which usually con-tain, a~ e3sential component~, water, finely divided inorganic or organic pigment~ (eg. iron oxide, titanium dioxide, azo pigments, phthalocyanine~ or carbon black), di~persant~ or, if required, thickeners, ~uch as casein, thermoplastic or nonthermopla~ic binder and fur~her assistant3~ such a~ preservative~, are generally stirred into the synthetic re~in dispersions serving as binders.
The colored leather protective formulations thus obtainabls are applied to the leather by curtain coating, knife coating, ~preading, spraying or brushing or by the plush proces~. In general, a base protective coat is ir~t applied, ironing i~ carried out and a top coat of the ~ame composition is then applied. After drying of the top coat i8 complete, nitrocellulose or other cellu-lose esters are among the suitable binder-containing ~easons ~or imparting the desired glo~s or physical - 6 - O.Z. 0050/40587 fastness properties to the protective coat.
EXAMPLES
Preparation of various synthetic resin dispersions Bl ~o A mixture of 12 g of sodium peroxydisulfate, 1.6 kg of water and 9.1% of feed 1 was initially taken in a pressure vessel and heated to the polymerization tempera-ture of 55C in the course of 30 minute~. Thereafter, the remaining amount of feed 1 was introduced in the course of 6 hours via a feed vecsel 1 while maintaining the polymerization temperature, the said feed 1 being supplemented duriny the final two hour~ by feed 2 intro-duced via a feed vessel 2. After the end of the monomer feed, polymerization was continued for a further 8.5 hours. The ~olids content of the resulting dispersion was 38.6% by weight.
Feed 1:
3.4 kg of water, 2.2 kg of butadiene, 1.O kg of acrylonitrile, 200 g of methacrylamide, 500 q of 15~ ~trength by weight aqueous ~olution of Na n-lau~ylsulfate (émulsifier I), 140 g of a mixture of ethoxylated linear Cl~-Cl8-alkanolQ
(degree of ethoxylation 50, emulsifier II), 12 g of tetrasodium dispho~phate and 32 g of tert-dodecyl mercaptan ~eed 2:
269 g of water, 403 g of ~tyrene, 201 g of methacrylic acid and 27 g of emul~ifier I
A mixture of 12.6 g of sodium peroxydisulfate, 1.68 kg of water and 9% of feed 1 wa~ initially taken in - .
~':
.
2(~ 8~
_ 7 _ o.z. 0050/40587 a pressure vessel and heated to the polymerization temperature of 55C in the course of 30 minutes. There-after, the remaining amount of feed 1 was introduced in the course of 6 hours while maintaining the polymeriza-tion temperature. After the end of the introduction offeed 1, feed 2 was introduced in the course of 30 minutes. Polymerization wa~ then continued for a further 8.5 hour~. The resulting disperRion had a solids content of 34.2~ by weight.
Feed 1:
3.1 Xg of water, 2.3 kg of butadiene, 1.O kg of acrylonitrile, 200 g of styrene, ~00 g of methacrylamide, 530 g of emul~ifier I, 420 g of a 20~ strength by weight aqueous solution of ethoxylated isooctylphenol (degree of ethoxylation 25, emul~ifiar III), 12.6 g of tetrasodium disphosphate and 33.5 g of tert-dodecyl mercaptan Feed 2: -210 g of ~tyrene and 210 g of methacrylic acid A mixture of 12 g of ~odium peroxydisulfate, 1.6 kg of water and 5.8~ of feed 1 was initially taken in a pre~ure vessel and heated to the polymerization tempera-ture of 5SC in the cour3e of 30 minute Thereafter, the remaining amount of feed 1 wa~ introduced in the cour~e of 3 hour~ via a feed ve~sel 1 while maintaining tho pol~meri~ation temperature, the said feed 1 being supplemented during the final hour by feed 2 introduced via a feed ve~el 2. After the end of the monomer feed, polymerization wa~ con~inued for a further 8.5 hours.
The resulting dispersion had a solids content of 38.7% by weight.
` - 8 - O.Z. 0050/40587 Feed 1:
3.4 kg of water, 2.2 kg of butadiene, 1.4 kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 540 g of emul~ifier I, 140 g of emulsifier II, 12 g of tetra~odium disphosphate and 32 g of tert-dodecyl mercaptan Feed 2:
263 g of water and 201 g of methacrylic acid A mixture of 11.9 g of sodium peroxydisulfate, 1.59 kg of water and 8.9~ of feed 1 was initially taken in a pxessure ves~el and heated to the polymeriæation temperature of 65C in the course of 30 minutes. There-after, the remaining amount of feed 1 wa~ introduced in the course of 6 hours via a feed vessel 1 while maintain-ing the polymerization temperature, the said feed 1 being supplemented during the final 30 minutes by the feed 2 introduced ~ia a feed vessel 2. Before the beginning of feed 2, a solution of 1.8 g of sodium peroxydisulfate in 176 g of water was added all at once to the reaction mix-ture. After the end of the monomer feed, polymerizationwa~ continued for a further 6 hour A di~per~ion having a solids content of 3g.4% by weight wa~ obtained.
Fsed ls 3.3 kg of watsr, 2.2 kg of butadiene, 1.O kg of acrylonitrile, 200 g of tyrene, 200 g of methacrylamide, 480 g of emulsifier I, 140 g of emulsifier II, 12 g of tetrasodium disphosphate and , 2~q~9~
~- - 9 - O.Z. 0050/40587 40 g of dodecyl mercaptan Feed Z:
264 g of water, 198 g of methacrylic acid, 198 g of methyl methacrylate and 26.4 g of emulsifier I
A mixture of 12.1 g of sodium peroxydisulfate, 1.59 kg of water and 8.7~ of feed 1 wa~ initially taken in a pressure vessel and heated to the polymerization temperature of 55C in the course of 30 minute~. There-after, the remaining amount of feed 1 was introduced in the cour~e of 6 hours while maintaining the polymeriza-tion temperature, followed by the addition of 202 g of styrene as feed 2 in the course of 30 minute~. After th~
end of the monomer addition, polymerization was cnntinued for a further 8.5 hours.
Feed 1:
3.4 kg of water, 2.2 kg of butadiene, 1.O kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 500 g of emulsifier I, 400 g of emulsifier III, 12 g of tetrasodium disphosphate and 32 g of tert-dodecyl mercaptan A mixture of 10.6 g of sodium peroxydisulfate, 1.6 kg of water and 9.4~ of feed l was initially taken in a pressure ves~el and heated to the polymerization temperature of 55C in the course of 30 minutes. There-after, the remaining amount of feed 1 was added in the cour~a o~ 6 hour via a feed vessel 1 while maintaining the polymerization temperature, the Yaid feed 1 being supplemented during the final 30 minutes by feeds 2 and 3 introduced via a feed vessel~ 2 and 3. After the end , 2~
- - 10 - O.Z. 0050/40587 of the monomer addition, polymerization was continued for a further 7.5 hours. The solids content of the resulting dispersion was 40.1% by weight.
Feed 1:
2.9 kg of water, 2.3 kg of butadiene, 1.O kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 520 g emulsifier I, 310 g of a 20% ~trength by weight aqueous solution of a mi~ture of ethoxylated linear C~2- or C1b-alkanol~ (degree of ethoxylation 20, emul~ifier IV), 12 g of tetra~odium disphosphate and 33.3 g of tert-dodecyl mercaptan Feed 2:
269 g of water, 208 g of methacrylic acid 208 g of methyl methacrylate and 26 g of emulsifier I
Feed 3:
A ~olution o~ 1.85 g of sodium peroxydisulfate in 109 g of water.
A mixture of 10.32 g of sodium peroxydisulfate, 1.62 kg of water and 9.1~ of feed 1 was initially taken in a pressure ves~el and heated to the polymerization temperature of 55C in the course of 30 minute~. There-after, the remaining amount of feed 1 was introduced in the course of 5.5 hours while maintaining ~he poly-merization temperature. After the end of the addition of feed 1, feed 2 wa~ introduced in the cour~e of 30 minute~. Before the beginning of feed 2, a ~olution of 1.8 g of ~odium peroxydisulfa~e in 180 g of water was added all at once to the reaction mixture. After the end of the monomer addition, polymerization wa~ continued for a further 6 hour~. The resul~ing disper~ion had a ~olid~
' ~ ~
, '~
, ;~ 82 ~ O.Z. 0050/40587 content of 37.9% by weight.
Feed 1:
3.2 kg of water, 2.2 kg of butadiene, 1.0 kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 480 g of emulsifier I, 140 g of emul4ifier II, 12 g of tetrasodium disphosphate and 32 g of dodecyl mercaptan Feed 2:
269 g of water, 202 g of methacrylic acid 202 g of styrene and 227 g of emul~ifier I
A mixture of 12 g of sodium peroxydisulfate, 1.6 kg of water and 8.9% of feed 1 was initially taken in a pressure ve~sel and heated to the polymerization tempera-ture of 55C in the course of 30 minutes. Thereafter, 5/6 of the remaining amount of feed 1 were introduced in the course of 5 hour~ via a feed vessel 1 while maintain-ing the polymerization temperature. ~eed 2 wa~ then mixed with the 1/6 of feed 1 remaining in feed ves~el 1, and the mixtura obtained wa3 fed into the reaction mix-ture in the cour~e of 1 hour. After the end of the monomsr addition, polymerization was continued for a further 8.5 hours. The solids content of the resultin~
dispersion wa~ 39.2% by weight.
Testing of variou~ leather protective coat~
100 g of an aqueous pigment formulation which contalned, as essential component3, 12% by weiqht of finely divided carbon black, 85% by waight of water and 2.5% by weight of a disper~ant were stirred into 400 g of each of the dispersion~ Bl to B3 and B7 and B~ 9 whose - , .
8;~
- 12 - O.Z. 0050/40587 solids content had been brought to 30% by weight beforehand by dilution with water. 20 g/m2 of the form-ulations obtained were applied to buffed box leather with the aid of a mold board covered with absorptive plush and hot-pressed at 90C. Thereafter, a further 4 g/m2 of the same formulations were applied using the plush pad, and the residual amount then still required for complete coverage was applied by spraying. Thereafter, drying was carried out at 80~C in the air and a season containing nitrocellulose as a binder was applied. The low temper-ature breaking qtrength, the dry flexing resistance (50,000 flexes with a Bally flexometer) and the wet flexing resistance (20,000 flexes with a Bally flex-ometer) were then determined for the leather protective coats produced in this manner, by the methods of the International Union of Leather Chemists ~ssociations (I.U.P. Methods). The results are shown in Table 1.
Table l also contains the result of a Comparative Experi-ment V1, in which a mixture containing 5 parts of latex A and 1 part of ZnO-containing paste A according to EP-B
29170 wa~ used instead of a novel dispersion.
.
. .
- 13 - O. Z . 0050/40587 t~ O
u~
'~ ~ O
~o ~o tn ~ ra o o a~
~o m o .,~
~o In .,1 ~ ~ ~
,, a ~ o o m E~ ~0 ~ ~0 ~o ~ ~o ~n m 3~ ~ 3 W
3 ~ ~ ~
m ~ il:
(degree of ethoxylation 50, emulsifier II), 12 g of tetrasodium dispho~phate and 32 g of tert-dodecyl mercaptan ~eed 2:
269 g of water, 403 g of ~tyrene, 201 g of methacrylic acid and 27 g of emul~ifier I
A mixture of 12.6 g of sodium peroxydisulfate, 1.68 kg of water and 9% of feed 1 wa~ initially taken in - .
~':
.
2(~ 8~
_ 7 _ o.z. 0050/40587 a pressure vessel and heated to the polymerization temperature of 55C in the course of 30 minutes. There-after, the remaining amount of feed 1 was introduced in the course of 6 hours while maintaining the polymeriza-tion temperature. After the end of the introduction offeed 1, feed 2 was introduced in the course of 30 minutes. Polymerization wa~ then continued for a further 8.5 hour~. The resulting disperRion had a solids content of 34.2~ by weight.
Feed 1:
3.1 Xg of water, 2.3 kg of butadiene, 1.O kg of acrylonitrile, 200 g of styrene, ~00 g of methacrylamide, 530 g of emul~ifier I, 420 g of a 20~ strength by weight aqueous solution of ethoxylated isooctylphenol (degree of ethoxylation 25, emul~ifiar III), 12.6 g of tetrasodium disphosphate and 33.5 g of tert-dodecyl mercaptan Feed 2: -210 g of ~tyrene and 210 g of methacrylic acid A mixture of 12 g of ~odium peroxydisulfate, 1.6 kg of water and 5.8~ of feed 1 was initially taken in a pre~ure vessel and heated to the polymerization tempera-ture of 5SC in the cour3e of 30 minute Thereafter, the remaining amount of feed 1 wa~ introduced in the cour~e of 3 hour~ via a feed ve~sel 1 while maintaining tho pol~meri~ation temperature, the said feed 1 being supplemented during the final hour by feed 2 introduced via a feed ve~el 2. After the end of the monomer feed, polymerization wa~ con~inued for a further 8.5 hours.
The resulting dispersion had a solids content of 38.7% by weight.
` - 8 - O.Z. 0050/40587 Feed 1:
3.4 kg of water, 2.2 kg of butadiene, 1.4 kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 540 g of emul~ifier I, 140 g of emulsifier II, 12 g of tetra~odium disphosphate and 32 g of tert-dodecyl mercaptan Feed 2:
263 g of water and 201 g of methacrylic acid A mixture of 11.9 g of sodium peroxydisulfate, 1.59 kg of water and 8.9~ of feed 1 was initially taken in a pxessure ves~el and heated to the polymeriæation temperature of 65C in the course of 30 minutes. There-after, the remaining amount of feed 1 wa~ introduced in the course of 6 hours via a feed vessel 1 while maintain-ing the polymerization temperature, the said feed 1 being supplemented during the final 30 minutes by the feed 2 introduced ~ia a feed vessel 2. Before the beginning of feed 2, a solution of 1.8 g of sodium peroxydisulfate in 176 g of water was added all at once to the reaction mix-ture. After the end of the monomer feed, polymerizationwa~ continued for a further 6 hour A di~per~ion having a solids content of 3g.4% by weight wa~ obtained.
Fsed ls 3.3 kg of watsr, 2.2 kg of butadiene, 1.O kg of acrylonitrile, 200 g of tyrene, 200 g of methacrylamide, 480 g of emulsifier I, 140 g of emulsifier II, 12 g of tetrasodium disphosphate and , 2~q~9~
~- - 9 - O.Z. 0050/40587 40 g of dodecyl mercaptan Feed Z:
264 g of water, 198 g of methacrylic acid, 198 g of methyl methacrylate and 26.4 g of emulsifier I
A mixture of 12.1 g of sodium peroxydisulfate, 1.59 kg of water and 8.7~ of feed 1 wa~ initially taken in a pressure vessel and heated to the polymerization temperature of 55C in the course of 30 minute~. There-after, the remaining amount of feed 1 was introduced in the cour~e of 6 hours while maintaining the polymeriza-tion temperature, followed by the addition of 202 g of styrene as feed 2 in the course of 30 minute~. After th~
end of the monomer addition, polymerization was cnntinued for a further 8.5 hours.
Feed 1:
3.4 kg of water, 2.2 kg of butadiene, 1.O kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 500 g of emulsifier I, 400 g of emulsifier III, 12 g of tetrasodium disphosphate and 32 g of tert-dodecyl mercaptan A mixture of 10.6 g of sodium peroxydisulfate, 1.6 kg of water and 9.4~ of feed l was initially taken in a pressure ves~el and heated to the polymerization temperature of 55C in the course of 30 minutes. There-after, the remaining amount of feed 1 was added in the cour~a o~ 6 hour via a feed vessel 1 while maintaining the polymerization temperature, the Yaid feed 1 being supplemented during the final 30 minutes by feeds 2 and 3 introduced via a feed vessel~ 2 and 3. After the end , 2~
- - 10 - O.Z. 0050/40587 of the monomer addition, polymerization was continued for a further 7.5 hours. The solids content of the resulting dispersion was 40.1% by weight.
Feed 1:
2.9 kg of water, 2.3 kg of butadiene, 1.O kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 520 g emulsifier I, 310 g of a 20% ~trength by weight aqueous solution of a mi~ture of ethoxylated linear C~2- or C1b-alkanol~ (degree of ethoxylation 20, emul~ifier IV), 12 g of tetra~odium disphosphate and 33.3 g of tert-dodecyl mercaptan Feed 2:
269 g of water, 208 g of methacrylic acid 208 g of methyl methacrylate and 26 g of emulsifier I
Feed 3:
A ~olution o~ 1.85 g of sodium peroxydisulfate in 109 g of water.
A mixture of 10.32 g of sodium peroxydisulfate, 1.62 kg of water and 9.1~ of feed 1 was initially taken in a pressure ves~el and heated to the polymerization temperature of 55C in the course of 30 minute~. There-after, the remaining amount of feed 1 was introduced in the course of 5.5 hours while maintaining ~he poly-merization temperature. After the end of the addition of feed 1, feed 2 wa~ introduced in the cour~e of 30 minute~. Before the beginning of feed 2, a ~olution of 1.8 g of ~odium peroxydisulfa~e in 180 g of water was added all at once to the reaction mixture. After the end of the monomer addition, polymerization wa~ continued for a further 6 hour~. The resul~ing disper~ion had a ~olid~
' ~ ~
, '~
, ;~ 82 ~ O.Z. 0050/40587 content of 37.9% by weight.
Feed 1:
3.2 kg of water, 2.2 kg of butadiene, 1.0 kg of acrylonitrile, 200 g of styrene, 200 g of methacrylamide, 480 g of emulsifier I, 140 g of emul4ifier II, 12 g of tetrasodium disphosphate and 32 g of dodecyl mercaptan Feed 2:
269 g of water, 202 g of methacrylic acid 202 g of styrene and 227 g of emul~ifier I
A mixture of 12 g of sodium peroxydisulfate, 1.6 kg of water and 8.9% of feed 1 was initially taken in a pressure ve~sel and heated to the polymerization tempera-ture of 55C in the course of 30 minutes. Thereafter, 5/6 of the remaining amount of feed 1 were introduced in the course of 5 hour~ via a feed vessel 1 while maintain-ing the polymerization temperature. ~eed 2 wa~ then mixed with the 1/6 of feed 1 remaining in feed ves~el 1, and the mixtura obtained wa3 fed into the reaction mix-ture in the cour~e of 1 hour. After the end of the monomsr addition, polymerization was continued for a further 8.5 hours. The solids content of the resultin~
dispersion wa~ 39.2% by weight.
Testing of variou~ leather protective coat~
100 g of an aqueous pigment formulation which contalned, as essential component3, 12% by weiqht of finely divided carbon black, 85% by waight of water and 2.5% by weight of a disper~ant were stirred into 400 g of each of the dispersion~ Bl to B3 and B7 and B~ 9 whose - , .
8;~
- 12 - O.Z. 0050/40587 solids content had been brought to 30% by weight beforehand by dilution with water. 20 g/m2 of the form-ulations obtained were applied to buffed box leather with the aid of a mold board covered with absorptive plush and hot-pressed at 90C. Thereafter, a further 4 g/m2 of the same formulations were applied using the plush pad, and the residual amount then still required for complete coverage was applied by spraying. Thereafter, drying was carried out at 80~C in the air and a season containing nitrocellulose as a binder was applied. The low temper-ature breaking qtrength, the dry flexing resistance (50,000 flexes with a Bally flexometer) and the wet flexing resistance (20,000 flexes with a Bally flex-ometer) were then determined for the leather protective coats produced in this manner, by the methods of the International Union of Leather Chemists ~ssociations (I.U.P. Methods). The results are shown in Table 1.
Table l also contains the result of a Comparative Experi-ment V1, in which a mixture containing 5 parts of latex A and 1 part of ZnO-containing paste A according to EP-B
29170 wa~ used instead of a novel dispersion.
.
. .
- 13 - O. Z . 0050/40587 t~ O
u~
'~ ~ O
~o ~o tn ~ ra o o a~
~o m o .,~
~o In .,1 ~ ~ ~
,, a ~ o o m E~ ~0 ~ ~0 ~o ~ ~o ~n m 3~ ~ 3 W
3 ~ ~ ~
m ~ il:
Claims (3)
1. An aqueous synthetic resin dispersion obtainable by copolymerizing A) from 70 to 97.5 parts by weight of a monomer mixture containing a) from 40 to 75% by weight of butadiene (monomer I), b) from 25 to 60% by weight of acrylonitrile (monomer II), c) from 0 to 25% by weight of styrene (monomer III), d) from 0 to 10% by weight of one or more amides of .alpha.,.beta.-monoethylenically unsaturated monocarboxylic acids of 3 to 5 carbon atoms (monomers IV) and e) from 0 to 10% by weight of other copolymerizable monomers (monomers V) and B) from 2.5 to 30 parts by weight of one or more co-polymerizable monovinyl compounds monomers VI) at from 30 to 70°C in aqueous emulsion so that not less than 50% by weight of the monomer mixture A is prepoly-merized to a conversion of not less than 80%, and then continuing the polymerization with the addition of the remaining monomers A and the monomers B.
2. A process for the preparation of an aqueous syn-thetic resin dispersion by copolymerization of A) from 70 to 97.5 parts by weight of a monomer mixture containing a) from 40 to 75% by weight of butadiene (monomer I), b) from 25 to 60% by weight of acrylonitrile (monomer II), c) from 0 to 25% by weight of styrene (monomer III), d) from 0 to 10% by weight of one or more amides of .alpha.,.beta.,monoethylenically unsaturated monocarboxylic acids of 3 to 5 carbon atoms (monomers IV) and e) from 0 to 10% by weight of other copolymerizable monomers (monomers V) and B) from 2.5 to 30 parts by weight of a mixture of co-polymerizable monovinyl compounds (monomers VI) in aqueous emulsion at from 30 to 70°C, wherein not less than 50% by weight of the monomer mixture A is prepoly-merized to a conversion of not less than 80%, and the polymerization is then continued with the addition of the remaining monomers A and the monomers B.
3. A method of using a synthetic resin dispersion as claimed in claim 1 as a binder for protective coats on leather.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3905010A DE3905010A1 (en) | 1989-02-18 | 1989-02-18 | AQUEOUS RESIN DISPERSION |
| DEP3905010.6 | 1989-02-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2009182A1 true CA2009182A1 (en) | 1990-08-18 |
Family
ID=6374417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002009182A Abandoned CA2009182A1 (en) | 1989-02-18 | 1990-02-02 | Aqueous synthetic resin dispersions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0384235B1 (en) |
| AU (1) | AU619386B2 (en) |
| CA (1) | CA2009182A1 (en) |
| DE (2) | DE3905010A1 (en) |
| ES (1) | ES2071689T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4141760A1 (en) * | 1991-12-18 | 1993-06-24 | Basf Ag | AQUEOUS POLYMER DISPERSION |
| DE102004028391A1 (en) * | 2004-06-14 | 2005-12-29 | Basf Ag | Process for the preparation of aqueous polymer dispersions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD114956A1 (en) * | 1974-11-04 | 1975-09-05 | ||
| DE3018385A1 (en) * | 1980-05-14 | 1982-01-21 | Bayer Ag, 5090 Leverkusen | METHOD FOR TREATING FIBER MATERIALS |
| DE3105779A1 (en) * | 1981-02-17 | 1982-09-02 | Bayer Ag, 5090 Leverkusen | AQUATIC DISPERSIONS, THEIR PRODUCTION AND USE |
| DE3688101T3 (en) * | 1985-05-10 | 2000-09-28 | Mitsubishi Rayon Co | Low gloss thermoplastic resin. |
-
1989
- 1989-02-18 DE DE3905010A patent/DE3905010A1/en not_active Withdrawn
-
1990
- 1990-02-02 CA CA002009182A patent/CA2009182A1/en not_active Abandoned
- 1990-02-09 EP EP90102534A patent/EP0384235B1/en not_active Expired - Lifetime
- 1990-02-09 DE DE59009037T patent/DE59009037D1/en not_active Expired - Fee Related
- 1990-02-09 ES ES90102534T patent/ES2071689T3/en not_active Expired - Lifetime
- 1990-02-16 AU AU49850/90A patent/AU619386B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0384235B1 (en) | 1995-05-10 |
| AU619386B2 (en) | 1992-01-23 |
| DE3905010A1 (en) | 1990-08-23 |
| ES2071689T3 (en) | 1995-07-01 |
| EP0384235A2 (en) | 1990-08-29 |
| AU4985090A (en) | 1990-08-23 |
| EP0384235A3 (en) | 1991-10-16 |
| DE59009037D1 (en) | 1995-06-14 |
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