CA2114688A1 - Copolymers based on maleic acid derivatives and vinyl monomers, their production and application - Google Patents
Copolymers based on maleic acid derivatives and vinyl monomers, their production and applicationInfo
- Publication number
- CA2114688A1 CA2114688A1 CA002114688A CA2114688A CA2114688A1 CA 2114688 A1 CA2114688 A1 CA 2114688A1 CA 002114688 A CA002114688 A CA 002114688A CA 2114688 A CA2114688 A CA 2114688A CA 2114688 A1 CA2114688 A1 CA 2114688A1
- Authority
- CA
- Canada
- Prior art keywords
- mole
- copolymers
- necessary
- mixture
- group
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
- C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
Abstract
Abstract Copolymers which are composed essentially of the structural elements A) B) a) b) and/or and/or c) C) and, if necessary, D) a) b) and/or
Description
211'1~
Copolymers Based on Maleic Acid Derivatives and Vinyl Monomers, their Production and Application The invention relates to copolymers based on maleic acid derivatives and vinyl monomers, their production and application, as well as b ~ er mixtures and building materials containing copolymers.
Copolymers based on maleic anhydride are known, for example, from the DE-A-33 44 470 and the US-PS 4,972,025 and are employed, among other things, as additives for hydraulic binders e.g. cement, anhydrite or plaster, in which they increase flowabili~y in particular during processing or improve the mechanical qualities of the hardened building material. Additives based on naphthalenesulphonic acid-formaldehyde condensates possess especially good flow properties, as described in the US-PS 4,725,665. These additives, designated as liquefiers, plasticisers, superpl~st$cisers, dispersing agents, or water reducing agents, possess the disadvantage, however, that the binder's flowability cannot be maintained for a sufficiently long period of time.
Since c,oncrete is increa~ingly delivered to the construction site as pre-mixed or ready-mixed concrete, this loss of ~orkability (slump loss) ~ithin a short period of time represents a problem which must be solved urgently.
Superplastici~e~sbased on maleic acid derivatives (from the US-PS
5,100,984 and DE-A-41 42 388) or those based on melamine and glyoxylic acid (from ~he DE-A-42 17 181) which already allow for a certain amount of control over the flow properties of cement mixture~ are known. However, the qualities of these cement mixtures are not sufficient for the actual increased demands. Also, the production of the s~arting materials employed is in part costly.
Consequently, the task ramain~ of finding improved additives in ~he area of binder liquefier~ and dispersing agents for solid matter suspensions which yield an optimum - ~ :
:: : : : ' ~ - , :
. - - ~ . , ~ :- , :
: ~-` 2 2~ g . .
combination of qualities, especially with regard to their flow and setting properties, and also with regard to the maintenance of their effectiveness in the event of relatively long periods of storage in the form of their aqueous preparations as well, i.e. especially those which are effective at dispersing and liquefying in binder suspensions ln particular and which enable optimum and practical control over the time frame of processing without at the same time excessively delaying the setting process.
It was found that new copolymers wi~h a special composition based on maleic acid, maleic esters, maleic amides, or maleic imide derivatives and vinyl polymers do not possess these disadvantages and yield the desired, positive qualities as additives to binders.
The object of the invention is therefore copolymers which are composed essentially of the structural elements .
i A~ ¦ ¦
COOM COO (C~m)nR
.
- CH CH - -. B) a) l l and/or b) CO CO I ~ 2 N COOM CONHR
,., ~
~ and/or c) ~ ~
~; .
s C) R4 ':~
: ' ~ ' ~ ' , ~ ~ 3 211~6~8 ~ and, if necessary, , .
D) a) - CH
~ ~ I b) _ c~ -- C~ -- CO CO and/or l I
\ / C~OM CGOM
-: O -:, . .
- whereby .~ ~
. M: represents H or a cation such as alkaline or alkaline-~ earth metal, an ammonium group, or the residue of an organic amino group, Rl: represents C1 to C2 0 alkyl, Cs to C8 cycloalkyl or aryl . group residue, .. R2: represents H, C1 to C20 alkyl or hydroxyalkyl, C~ to C8 . cycloalkyl or aryl group residue in which 1 or more H
atoms can be substituted by the structural elements -COOM, -S03M and/or PO3M2, as well as structural units of the General Formula (C~H2~0)n R1, which can repeat if necessary, R3: represents H, a methyl or methylene group which can be substituted if necessary and which forms a 5 to 8-member ring or an indene ring which R5 includes, R~: represents H, a methyl or ethyl group, Rs: represents H, Cl - C20 alkyl, Cg - C8 cycloalkyl or aryl group residue, which can be substituted if necessary, an alkoxy carbonyl group, an alkoxy group, an alkyl or aryl carboxylate group, a carboxylate group, a hydroxyalkoxy carbonyl group, m: represents a whole number from 2 to 4, n: .represents a whole number from O - 100, preferably from 1 - 20.
Mono- di- or trialkyl- or -alkanolamines with l to 8 C atoms are possible, for example, as residue M from organic amino groups. :.
,, :, :
211~fi~
The structural elements A, Ba, Bb, Bc, C and D respectively can represent uniform compositions; however, they can also be present as mixtures of various compositions. The mean mole-cular weight of the copolymers as claimed in the invention amounts to approximately 1000 to 100,000, preferably approxi-mately 2000 to 50,000 g/mole.
Preferably, the structural elements A amount to approximately 1 to 85, more preferably 20 to 55 mole ~ in the copolymers as claimed in the invention; preferably; the structural elements B amount to approximately 1 to 85, more preferably 2 to 25 mole ~; preferably, the structural elements C amount to approximately 1 to 90, more preferably 40 to 60 mole ~, and preferably, the structural elements D amount to 0 to 50, more preferably 1 to 10 mole ~. A composition of 35 to 40 mole ~ of the structural elements A, 5 to 10 mole % of the structural elements B, 50 mole % of the structural elements C and 2 to 5 mole % of the structural elements D have proven to be especially favorable. In the copolymers as claimed in the invention, 1:1 would be an especially advantageous molar ratio of the structural units (A + B + D) : C.
The starting products which make up the structural elements C
and D in the copolymer are employed in the form of the corresponding monomers G and H as claimed in the invention.
G R
c , Ha) C~ =~==C~ b) C~ _ CH
I and/or ¦ ~
C ~o COOM COCM
` O
,, On the other hand, the structural elements A and B can be employed either in the form of the preformed units E or F, , -.
- .: . ~ - . ~ ... . .
-v--~
211~8~
.
~ E C~ = C~
I ~1 COO(c~ 2~o)~
F a) I -- C~ and/or b) C~ ~ c~
Co Co COOM CCN~3R 2 N
.
and/or c) CH - Ch ox~ ~ONR2 : .
or they are formed during or after polymerization by means of a polymer analogous reaction. Structural element A
is composed of monoesterified dicarboxylic acid structures, whereby M preferably represents hydrogen or sodium; m preferably represents 2; n preferably represents 5 to 20, and R1 preferably represents a linear or branched alkyl group with 1 to 3 carbon atoms. More preferably, monoesterified maleic anhydride units with monomethoxypolyethylene glycol or monomethoxypolyethylene-block-propylene glycol with a mean molecular weight of 250 g/mole (n=5? to 750 g/mole (n=17).
The anhydride units remaining in the copolymer are represented by structural element D, which can, as claimed in the invention, be present either as anhydride ring Da) or in hydrolyzed form Db), whereby M preferably represents hydrogen or sodium. I
Structural unit B is present according to Formula Ba) as a 5-member, preferably N-substituted imide ring which can already be given by the structure of the monomers employed for the production of the copolymers, or which can be produced by means of the method as claimed in the invention through the conversion of compounds which carry primary amino groups with ~ ' ~ . : '. , ' : ' ,,',,,. -. , , . '. , ' ' '' ~'" ' ' '' 6 211~688 the anhydride group of the maleic anhydride. In this case, R2 is preferably a linear or branched C4 to C1 2 alkyl group, a cyclohexyl ring, a phenyl or naphthyl group, substituted if necessary, or a linear or branched, terminally closed poly-oxyalkylene glycol of the General Formula (CmH2mO)nR1 with m =
Copolymers Based on Maleic Acid Derivatives and Vinyl Monomers, their Production and Application The invention relates to copolymers based on maleic acid derivatives and vinyl monomers, their production and application, as well as b ~ er mixtures and building materials containing copolymers.
Copolymers based on maleic anhydride are known, for example, from the DE-A-33 44 470 and the US-PS 4,972,025 and are employed, among other things, as additives for hydraulic binders e.g. cement, anhydrite or plaster, in which they increase flowabili~y in particular during processing or improve the mechanical qualities of the hardened building material. Additives based on naphthalenesulphonic acid-formaldehyde condensates possess especially good flow properties, as described in the US-PS 4,725,665. These additives, designated as liquefiers, plasticisers, superpl~st$cisers, dispersing agents, or water reducing agents, possess the disadvantage, however, that the binder's flowability cannot be maintained for a sufficiently long period of time.
Since c,oncrete is increa~ingly delivered to the construction site as pre-mixed or ready-mixed concrete, this loss of ~orkability (slump loss) ~ithin a short period of time represents a problem which must be solved urgently.
Superplastici~e~sbased on maleic acid derivatives (from the US-PS
5,100,984 and DE-A-41 42 388) or those based on melamine and glyoxylic acid (from ~he DE-A-42 17 181) which already allow for a certain amount of control over the flow properties of cement mixture~ are known. However, the qualities of these cement mixtures are not sufficient for the actual increased demands. Also, the production of the s~arting materials employed is in part costly.
Consequently, the task ramain~ of finding improved additives in ~he area of binder liquefier~ and dispersing agents for solid matter suspensions which yield an optimum - ~ :
:: : : : ' ~ - , :
. - - ~ . , ~ :- , :
: ~-` 2 2~ g . .
combination of qualities, especially with regard to their flow and setting properties, and also with regard to the maintenance of their effectiveness in the event of relatively long periods of storage in the form of their aqueous preparations as well, i.e. especially those which are effective at dispersing and liquefying in binder suspensions ln particular and which enable optimum and practical control over the time frame of processing without at the same time excessively delaying the setting process.
It was found that new copolymers wi~h a special composition based on maleic acid, maleic esters, maleic amides, or maleic imide derivatives and vinyl polymers do not possess these disadvantages and yield the desired, positive qualities as additives to binders.
The object of the invention is therefore copolymers which are composed essentially of the structural elements .
i A~ ¦ ¦
COOM COO (C~m)nR
.
- CH CH - -. B) a) l l and/or b) CO CO I ~ 2 N COOM CONHR
,., ~
~ and/or c) ~ ~
~; .
s C) R4 ':~
: ' ~ ' ~ ' , ~ ~ 3 211~6~8 ~ and, if necessary, , .
D) a) - CH
~ ~ I b) _ c~ -- C~ -- CO CO and/or l I
\ / C~OM CGOM
-: O -:, . .
- whereby .~ ~
. M: represents H or a cation such as alkaline or alkaline-~ earth metal, an ammonium group, or the residue of an organic amino group, Rl: represents C1 to C2 0 alkyl, Cs to C8 cycloalkyl or aryl . group residue, .. R2: represents H, C1 to C20 alkyl or hydroxyalkyl, C~ to C8 . cycloalkyl or aryl group residue in which 1 or more H
atoms can be substituted by the structural elements -COOM, -S03M and/or PO3M2, as well as structural units of the General Formula (C~H2~0)n R1, which can repeat if necessary, R3: represents H, a methyl or methylene group which can be substituted if necessary and which forms a 5 to 8-member ring or an indene ring which R5 includes, R~: represents H, a methyl or ethyl group, Rs: represents H, Cl - C20 alkyl, Cg - C8 cycloalkyl or aryl group residue, which can be substituted if necessary, an alkoxy carbonyl group, an alkoxy group, an alkyl or aryl carboxylate group, a carboxylate group, a hydroxyalkoxy carbonyl group, m: represents a whole number from 2 to 4, n: .represents a whole number from O - 100, preferably from 1 - 20.
Mono- di- or trialkyl- or -alkanolamines with l to 8 C atoms are possible, for example, as residue M from organic amino groups. :.
,, :, :
211~fi~
The structural elements A, Ba, Bb, Bc, C and D respectively can represent uniform compositions; however, they can also be present as mixtures of various compositions. The mean mole-cular weight of the copolymers as claimed in the invention amounts to approximately 1000 to 100,000, preferably approxi-mately 2000 to 50,000 g/mole.
Preferably, the structural elements A amount to approximately 1 to 85, more preferably 20 to 55 mole ~ in the copolymers as claimed in the invention; preferably; the structural elements B amount to approximately 1 to 85, more preferably 2 to 25 mole ~; preferably, the structural elements C amount to approximately 1 to 90, more preferably 40 to 60 mole ~, and preferably, the structural elements D amount to 0 to 50, more preferably 1 to 10 mole ~. A composition of 35 to 40 mole ~ of the structural elements A, 5 to 10 mole % of the structural elements B, 50 mole % of the structural elements C and 2 to 5 mole % of the structural elements D have proven to be especially favorable. In the copolymers as claimed in the invention, 1:1 would be an especially advantageous molar ratio of the structural units (A + B + D) : C.
The starting products which make up the structural elements C
and D in the copolymer are employed in the form of the corresponding monomers G and H as claimed in the invention.
G R
c , Ha) C~ =~==C~ b) C~ _ CH
I and/or ¦ ~
C ~o COOM COCM
` O
,, On the other hand, the structural elements A and B can be employed either in the form of the preformed units E or F, , -.
- .: . ~ - . ~ ... . .
-v--~
211~8~
.
~ E C~ = C~
I ~1 COO(c~ 2~o)~
F a) I -- C~ and/or b) C~ ~ c~
Co Co COOM CCN~3R 2 N
.
and/or c) CH - Ch ox~ ~ONR2 : .
or they are formed during or after polymerization by means of a polymer analogous reaction. Structural element A
is composed of monoesterified dicarboxylic acid structures, whereby M preferably represents hydrogen or sodium; m preferably represents 2; n preferably represents 5 to 20, and R1 preferably represents a linear or branched alkyl group with 1 to 3 carbon atoms. More preferably, monoesterified maleic anhydride units with monomethoxypolyethylene glycol or monomethoxypolyethylene-block-propylene glycol with a mean molecular weight of 250 g/mole (n=5? to 750 g/mole (n=17).
The anhydride units remaining in the copolymer are represented by structural element D, which can, as claimed in the invention, be present either as anhydride ring Da) or in hydrolyzed form Db), whereby M preferably represents hydrogen or sodium. I
Structural unit B is present according to Formula Ba) as a 5-member, preferably N-substituted imide ring which can already be given by the structure of the monomers employed for the production of the copolymers, or which can be produced by means of the method as claimed in the invention through the conversion of compounds which carry primary amino groups with ~ ' ~ . : '. , ' : ' ,,',,,. -. , , . '. , ' ' '' ~'" ' ' '' 6 211~688 the anhydride group of the maleic anhydride. In this case, R2 is preferably a linear or branched C4 to C1 2 alkyl group, a cyclohexyl ring, a phenyl or naphthyl group, substituted if necessary, or a linear or branched, terminally closed poly-oxyalkylene glycol of the General Formula (CmH2mO)nR1 with m =
2 - 4, n = O - 100 and R1 = C1 - C2 o alkyl, C5 - CB cycloalkyl or aryl. R2 residues which carry hydrophile groups, preferably sulphonic acid groups, are especially preferable. The following are examples of the preformed monomers which supply structural element B: N-phenylmaleimide, N-(2,6-dimethylphe-nyl)maleimide, N-hydroxyethylmaleimide, N-(4-sulphophenyl)-maleimide. The following are examples of compounds which form structural element C in the course of the method as claimed in the invention through a reaction with the anhydride units:
cyclohexylamine, 2-ethylhexylamine, n-laurylamine, glutamic acid, glycine, ~orpholine, sulphanilic acid, taurine, naph-thylaminesulphonic acid, naphthylaminedisulphonic acid, amino-ethanephosphonic acid and phosphanilic acid. Structural unit B
can also be present in the form of a corresponding semi-amide according to the formulas Bb and Bc.
The G monomers which produce structural element C are preferably compounds which possess a strong tendency to copolymerizate with maleic anhydrides. Examples of such monomers are: ethylene, propylene, n-butene, 2-methylpropene, diiso-2-methylpropene, cyclohexene, ~tyrene, alpha-methyl-styrene, indene, 4-methoxy~tyrene, 4-methylstyrene, ~inyl ace-tate, vinyl propionate, methylvinylether, ethylvinylether, isobutylvinylether, tetrahydrophthalic anhydride, n-butyl acrilate, methyl methacrylate, hydroxymethyl methacrylate or methacrylic acid.
These monomer~ or ~tr~ctural elements can, if necessary, al80 be employed in mixtures with one another or with other monomers.
A further object of the invention is a method for the production of copolymars characterized by the structural units : .
7 2~ 8 A to D which dispenses with the otherwise common organic : solvents, whereby a high yield of the copolymers are produced ~ with a method which is easy to use. For the production of the :: copolymers, a) one starts with a maleic acid semi-ester according to Formula E) or a mixture of a polyalkylene glycol monoether and maleic anhydride, which also reacts to the ~: maleic acid semi-ester according to Formula E at approximately 100 to 140C when an esterification catalyst is employed, or a mixture of maleic acid semi-ester, polyalkylene glycol monoether and maleic ~: anhydride, b) the monomer components according to Formula F or their ~ starting subs~ances, G and, if necessary, H, as well as .' more polyalkylene glycol monoethèr if necessary, as well .~ as common polymerization aids if necessary are added at . approximately 40 to 120C while being agitated, c) agitation of the mixture is continued at 40 to 150-C in :~ order to complete the polymerization reaction and the .~ polymer analogous conversion, and d) after cooling to approximately 50 to 80 C,.the reaction Z., mixture is normally neutralized with a base and diluted `.~ to the desired concentration with water.
.~
As claimed in the inventlon, either the polyalkylene glycol . monoether `required for the composition of the partial ~: structure A, or the macromer maleic acid semi-ester obtained in a previous reaction of maleic anhydride and the polyalkylene glycol monoether, or a mi~ture of both, may be .~ employed as a reaction medium. Preferably, the semi-e~ter i~
.. obtained at 120 - 140'C o~er a period of 2 to 4 hours, and -. preferably 0.5 to 1.0 w~ight ~ of an esterifying cataiyst such as ~ulphuric acid or toluene-p-sulphonic acid i.:employed. A~
claimed in the invention, a linear or branched alkoxypoly-`: alkylene glycol amine required for the composition of the partial structure B or .a mixture of polyalkylene glycol monoether and polyalkylene glycol amine monoether may be used . as a reaction medium.
.
, ..
,~;
., ,''~, ' .
8 ~ 6 8 ~
The bonding of structural elements A to D is preferably performed in such a way that one starts with a portion or all of the polyalkylene glycol monoether, which is mixed with a portion or all of the maleic anhydride. After completion of the previous reaction under the conditions described above, performed if necessary, the polymerization initiator is set and copolymerization is performed by adding the monomers which form structural units C, which can contain the polymerization initiator in a dissolved form if necessary. This inflow of monomers, however, can also contain the monomers which supply structural units B in the event that they are not miscible with one another. This method can, however, also be performed with 2 separate monomer inflows, preferably when the polymer analogous formation of structural element B
is impossible due to the insolubility of the amino compound in the polymer, such as when sulphanilic acid is employed.
Common additives such as those known to polymerization technology experts ~an be used as polymerization aids.
Preferably, these are polymerization initiators such as azo~isisobutyronitrile, azobis~2-methylvaleronotrile, dibenzo-yl peroxide, lauroyl peroxide, dicyclohexylpero20dicarbonate, tertiary butyl peroxy-2-ethylhexanoate and tertiary butyl perbenzoate, as well as polymerization accelerators or activators such as sodium bisulphitej ascorbic acid or salts from heavy metals, or molecular weight controllers such as dodecanethiol, tertiary dodecanethiol or diisopropylxanthogen disulphite.
Preferably, the polymerization reactions are performed at temperatures of approximately 40 to 120, more preferably at 60 to 100'C. The temperature~ for the subsequent reaction for completing the formation ~f esters, s~mi amide~, and/or imides are preferably 100 to 150-C.
In an especially preferred method of producing copolymers according to the invention, . ~ , . ..
~, 8a 2 1 1 4 6 ~ ~
a) one starts with a mixture of a polyalkylene glycol monoether of for-mula HO(CmH2mO)n R and a molar deficit of maleic anhydride, b) a mixture of a solution of an amine of formula NH2R or NHR2 in polyalkylene glycol monoether to which maleic anhy-dride is added while being agitated, a monomer component according to Formula G, if necessary by dbses from a separate inflow container, R
G) 13 l5 whereby M, R1, R2, R3, R~, R5, m and n have the meanings as described in Claim 1, as well as more polyalkylene glycol monoether if necessary, as well as common polymerization aids if necessary, are added at approximately 40 to 120-C while being agitated, c) the mixture is agitated further at 40 to 150'C to complete the polymerization reaction and the polymer ana-logous conversion, and d) the reaction mixture is normally neutralized with a base after cooling to approximately 50 to 80 C and diluted to the desired concentration with water.
i 211~68~
, ., `: ~
, .,~
When doing so, one starts with a partial amount of the polyalkylene glycol monoether required for the formation of structural element A together with a deficit of maleic anhydride. The monomer containing amino groups which is required for the composition of structural unit B, preferably ~-(4-sulphophenyl3maleic acid monoamide, is formed while being agitated in an agitable inflow container by dissolving 4-sulphanilic acid, which is preferably a salt, in the remaining amount of polyglycol and subsequently adding maleic anhydride.
The amount of initiator required for polymerization is also subsequently dissolved in this mixture. After the reactor receiver has been brought to polymerization temperature, the addition of the mixture is begun. At the same time, the addition of the monomers or monomer mixture required for the formation of structural element C from a separate inflow container is begun, and polymerization is conducted. After completion of polymerization, the polymer analogous esterification and , formation of amides or imides is completed at a higher temperature.
During polymerization, a vi~cous reaction ma~s is formed which is easily agitable a~d which is normally diluted with water after cooling to 50 - 80 C and neutralized by adding a ba~e, e.g.
an alk~line substance.
The method as claimed in the invention is characterized above all in that the yield is high, the residuai monomer propo* ion in the final product is low, and that it is simple, environ-mentally f~iendly, and safe.
lo 2 1 1 ~ 6 8 ~
All starting materials employed are components of the ~inal product, which is therefore free of undesirable solvent residues. At first, the polyalkylene glycol monoether serves as a reaction medium for the formation of certain monomers such as sulphophenyl maleic acid monoamide; later, it serves as a polymerization medium and has a positive effect on heat dissipation and agitability of the polymer. Finally, it is incorporated into the copolymer itself as a component via the free OH group. In contrast to known methods in which the production of carboxylic acid imide structures with substituents whlch carry sulphonic acid groups in polymers analogously to polymerization can be done only in an aqueous solution and under pressure and remains incomplete, the reaction is successful without pressure and produced a high yield with the aid of the method as claimed in the invention.
The copolymers as claimed in the invention are suitable as additives to aqueous suspensions of powdery substances such as clays, porcelain slips, silica flou~, chalk, carbon black, crushed rocks, pigments, talcum and plastic powders, though they are especially suitable for suspensions of hydraulic binders such as portland cement, portland blast-furnace cement, trass cement, fly-ash cement, aluminous cernent, magnesia cement, anhydrite or plaster in which they serve primarily as dispersing agents. Furthermore, the application or use of the ~opolymers as additives to hydraulic binders such as portland cement, portland blast-furnace cement, trass cement, fly-ash cement, anhydrite or plaster is preferable.
The copolymers as claimed in the invention can also be added to the hydraulic binders as a grinding aid for improving the grinding qualities, which means that the grinding process can be pl~nned mor!e efficiently.
.
The copolymers as claimed in the invention can be directly added to the cement mixtures such as cement masses, mortar or concrete in the form of their aqueous solutions or in anhydrous form in the amount of approximately O.O1 to 10 ~, preferably 0.05 to 3 ~ solid matter in relation to the weight --- 11 2114~8~
of the cement. Compared to the known additives, they demonstrate considerably increased dispersion, improved flow and setting qualities; they are free of formaldehyde and can maintain the flowability of the binder mixtures for a relatively long period of time. This means that the duration of processability of the binder mixtures can be increased with the aid of the copolymers as claimed in the invention due to the reduced slump loss. At the same time, however, the setting process of the finished building material is delayed only slightly. A further decisive advantage of the polymers according to the invention is that they do not lose their high initial ~ispersing power even after being stored for a relatively long period of time in the form of their aqueous preparations.
A further object of the invention are binder mixtures which contain hydraulic binders and the copolymers as claimed in the invention as well as water, common aggregates and additives, if necessary. A further object of the invention is a building material based on these binder mixtures.
A) Production ExamPles Example 1:
In a reaction container with a thermometer, agitator, ga~-entry tube, reflux condenser and 2 connections for separate inflow~, one starts with 282 g of methoxypolyethylene glycol (~oechst company) with a mean molecular weight (M) of 500 g/mole (0.564 mole) and mixes them with 6.1 g of maleic anhydride (0.062 mole) while agitating. The trapped air is replaced by ni!~rogen, and the contents of the flask are heated to 95 C.
At the same time, in a separate agitable inflow container (inflow 1) containing nitrogen, a solution of 282 g of methoxypolyethylene glycol (M ~ 500 g/mole, 0.564 mole) and 43.5 g of 4-sulphanilic acid-sodium salt dihydrate (0.188 .
:
12 ~ 8~
mole) is prepared, into which 122.8 g of maleic anhydride (1.253 mole) were introduced while agitating. When this was done, N-(4-sulphophenyl)maleic acid monoamide with an intense yellow coloration was obtained immediately, for which 15 mole % of the maleic anhydride employed was required.
Subsequently, 5.5 g of azobisisobutyronitrile (0.0335 mole) were added while being agitated, and this mixture was agitated until a completely clear solution was obtained. After the reaction temperature of 95C was reached in the polymerization container, the monomer solution which was prepared in the inflow container 1 and 137.1 g of styrene (1.318 mole) were added to the reactor from a second inflow container (inflow 2) by dose, continuously and simultaneously, over a period of 2 hours. After the addition process was complete, the mixture was agitated for another 2 hours at 95C, heated to 140C and agitated for a further 2 hours to complete esterification and the formation of imides.
The clear, orange-colored polymer melt was cooled to 50C
while being agitated and diluted by adding 130 g of distilled water. Subsequently, a pH value of 6.95 and a solid matter content of 36 weight ~ was achieved by adding 174 g of an a~ueous 20 % sodium hydroxide solution and 180 g of distilled water. A clear, yellowish-orange solution with a proportion of 0.39 weight ~ free styrene and a content of 0.17 weight maleic acid (determined by means of HPLC).
The mean molecular weight, determined by means of gel chromatography and using polyacrylic acid as a standard, amounted to 22,000 g/mole.
Example 2: I
The proce~ was similar to Example 1 with the difference that the inflows contained the following components:
nflow 1: 282.0 g methoxypolyethylene glycol (M=500 g/mole, 0.564 mole) ' 13 21146~
110.0 g malei,~ anhydride (1.122 mole) 3.1 g dodecanethiol 5.5 g azobisisobutyronitrile (0.0335 mole) Inflow 2: 125.5 g styrene (1.207 mole) 22.7 g N-phenylmaleimide (0.131 mole) After dilution and neutralization of the reddish-brown polymer melt, a clear, yellowish solution with a solid matter content of 33.9 weight %, 0.06 weight ~ non-converted styrene, 0.02 weight ~ free maleic acid and a mean molecular weight of the copolymer of 11,000 g/mole was obtained.
ExamPle 3:
Conversion as described in example 1 and 2 was repeated except that, instead of N-phenylmaleimide (Example 2), 26.3 g (0.131 mole) of N-(2,6-dimethylphenyl)maleimide, dissolved in 125.5 g of styrene, was employed. The final product, a clear, yellow aqueous solution, contained 34.4 weight % solid matter, 0.41 weight % free styrene and 0.17 weight % free maleic acid. The mean mol,scular weight amounted to 9,000 g/mole.
Example 4: ~
:- , Example 1 was repeated with the difference, however, that the N(4-sulphophenyl)maleic acid monoamide in inflow container 1 was employed as a preformed monomer in the form of a mononatrium salt in the amount of 35.7 g (0.122 mole). A
clear, yelIowish-orange copolymer solution with a solid matter co~tent of 36.0 weight ~, 0.2 weight ~ styr,sne, 0.07 weight ~
maleic acid and a mean molecular weight of 16,000 g/mole was obtained.
;
.~
.
~ . ..
- : ~:: - . :: -.
~ , ` 14 211~83 Example 5.
Copolymerization was repeated analogously to Example 1 with the following amounts and compositions of the inflows:
Inflow 1: 282.0 g methoxypolyethylene glycol (M=500 ~ g~mole, 0.564 mole) ; 122.8 g maleic anhydride (1.253 mole) 33.1 g 5-amino-2-naphthalenesulphonic acid-sodium salt (0.125 mole) 5.5 g azobisisobutyronitrile (0.0335 mole) Inflow 2: 137.1 g styrene (1.318 mole) The clear, deep brown polymer solution with a solid matter content of 35.9 weight % contained 0.22 weight ~ free styrene and 0.10 weight ~ free maleic acid at a mean molecular weight of 17,500 g/mole.
ExamPle 6:
Instead of 5-amino-2-naphthalenesulphonic acid-sodium salt as in Example 5, 43.6 g of 1-amino-3,6-naphthalenesulphonic acid-sodium salt (0.125 mole) was employed. The clear, blackish-brown polymer solution contained 35.5 weight ~ solid matter 0.37 weight % styrene and 0.21 weight ~ maleic acid and had a mean molecular weight of 19,500 g/mole.
Exam~le 7:
First, 600 g of methoxypol;yethylene glycol ~M = 500, 1.20 mole) were added to the same reaction container as described in Example 1 except with only one inflow connection, and 147 g of maleic anhydride (1.50 mole) were dissolved while being agitated. The trapped air was removed by rinsing with nitrogen, and the contents of the flask were heated to 95 C.
Subsequently, 156 g of styrene (1.50 mole) which contained t,~
21~8~
6.45 g of dissolved azobisisobutyronitrile (0.0393 mole) were added from an inflow container by uniform doses over a period of 2 hours, and the temperature was then held constant at 95~C
for a further 2 hours. Subsequently, a mixture of 11.1 g of butan-n-ol (0.15 mole) and 14.9 g of cyclohexylamine (0.15 mole) was added to the agitated reaction mass within 10 minutes, and the temperature was raised to 140C. After this temperature was reached, agitation was continued for another 2 hours at 140C to complete the formation of the esters and imides (analogous to polymerization), whereby a clear, deep orange polymer was obtained which was diluted with 1000 g of distilled water after cooling to 50C, adjusted to a pH value of 7.01 with 1~0 g of a 20 ~ sodium hydroxide solution at room temperature, and subsequently brought to a solid matter content of 36.1 weight ~ by adding a further 450 g of water.
The content of unconverted styrene was 0.58 weight ~; the free maleic acid content was 0.16 weight ~. The copolymer had a mean molecular weight of 23,000 g/mole.
ExamPle 8:
According to the method described in Example 7, except that instead of cyclohexylamine, 19.4 g (0.15 mole) of 2-ethylhexylamine were employed, and an aqueous copolymer solution with a solid matter content of 35.7 weight %, 0.22 weight ~ styrene, 0.22 weight % maleic acid and M=23,500 g/mole was obtained.
., .
Exam~le 9:
The method was analogous to Example 7, though with the followilhg changes:
.
Receiver: 500.0 g of methoxypolyethylene glycol (1.00 mole) 147.0 g of maleic anhydride (1.50 mole) .` :
'' ' : : ' -.". , -' : `
' 16 2i~46~
Before polymerization, the contents of the receiver were agitated for 1 hour at 130C
until partial esterification had taken place.
~nflow: 156.0 g styrene (1.50 mole) 6.45 g azobisisobutyronitrile (0.0393 mole) 3.6 g dodecanethiol After polymerization, imidization was performed by adding 24.5 g of cyclohexylamine (0.25 mole) and conducting a 2-hour conversion at 140C. The aqueous solution of the neutralized copolymer with a molecular weight of 2,500 g/mole was deep red and contained 37.0 weight % solid matter, 0.31 weight ~ free styrene and 0.03 weight % free maleic acid.
.
Example 10:
Example 9 was repeated with the difference that 32.3 g of 2-ethylhexylamine (0.25 mole) was employed instead of cyclohexamine. After processing, the copolymer with a mean molecular weight of 3,000 g/mole was present in the form of its sodium salt in an a~ueous solution with a solid matter content of 38.0 weight % and residual monomer proportions of 0.28 weight ~ styrene and 0.05 weight ~ maleic acid.
Exam~le 11:
Example 7 was repeated but with the following changes:
Receiver: 522 g methoxypolyethylene glycol (1.105 mole) 167 g ~ maleic anhydride (1.700 mole) Inflow: 221 g styrene (2.125 mole) 11.6 g dodecanethiol 9.7 g azobisisobutyronitrile 1.9 g azobiscyclohexanecarbonitrile ,~ ~ . . . ; . , : - . .
; . ~ i . - - : : ;
17 2~ 83 Polymerization was performed at lOSC with an inflow time of 60 minutes. After a subsequent reaction of 2 hours at 115C, 56.5 g of di-2-methoxyethylamine (0.425 mole) were added over a period of 15 minutes and agitated for 2 h at 140C to complete the ester and semi-amide formation. The crude product obtained was neutralized by adding water and Ca(OH)2.
., , ` Example 12:
The method was analogous to Example 11, although 28.3 g of di-2-methoxyethylamine were employed.
^ ExamPle 13:
Example 7 was repeated, but wlth the following changes:
.
Receiver: 600 g methoxypolyethylene-block-propylene glycol with a mean E0 value of 10 and 3 PO units (0.958 mole) 125 g maleic anhydride (1.278 mole) ;`
Inflow: 160 g styrene (1.534 mole~
8.6 g dodecanethiol 7.1 g azobisisobutyronitrile 1.4 g azobiscyclohexanecarbanitrile Polymerization was performed at 105-C. The inflow time amounted to 1 hour. After a subsequent reaction of 2 hours at 115-C, 17.0 g of di-2-methoxyethylamine (0.128 mole) were , added and agitated for another 2 hours at 140-C. A 40 %
.~ solution of ~he polymer was obtained Ly adding water and / calcium hydroxide.
' ' ' , ' ' ' . . , ~ , . . .
'j'': ~' ' ' ' ' ~' ~ ' ' ', 18 2tl~6~
Example 14:
Example 7 was repeated, but with the following changes:
Receiver: 455 g methoxypolyethylene glycol (0.910 mole) 137 g maleic anhydride (1.400 mole) Inflow: 182 g styrene (1.75 mole) 9.6 g dodecanethiol 8.0 g azobisisobutyronitrile 1.6 g azobiscyclohexanecarbonitrile Polymerization was performed at 105C (inflow time: 1 hour).
After a subsequent reaction of 120 minutes, 250 g of methoxypolyethylene glycol-block-propylene glycol amine with a mean EO value of 13 and a mean PO value of 3 units per mole were added over a period of 30 minutes. Afterwards, the reaction mixture was heated to 140C and agitated at 140C for 2 hours. Subsequently, the copolymer was cooled to lOO~C, diluted with water and neutralized with calcium hydroxide.
Control E~ample V1: -Commercial naphthalenesulphonic acid~formaldehyde polyconden-sate ("LIQUIMENT N" from Chemie Linz Ges.m.b.H.) Con~rol ExamPle V2:
Commercial melaminesulphonic acid-formaldehyde polycondensate ("LIQUIMENT MP-K" from Chemie Linz Ges.m.b.H.) , . ~
Control Exam~le V3:
According to the method described in the EP~A-402 563 tProduction Example 7), a copolymer was obtained from methoxy-polyethylene glycol monomaleate and N-vinyl pyrrolidone.
i . .
,= .
,, - : ~, 19 211~
Control ExamPle V4:
According to the method described in the EP-A-41 42 388 (Production Example 1), a copolymer was obtained from methoxypolyethylene glycol monomaleate and styrene.
B) APPlication E~mples The copolymers from examples 1 to 14 were subjected to comparative testing as a plasticiSer for cement mixtures in order to demonstrate their increased and longer lasting effectiveness in comparison to known plaSticisers According to DIN 1164/7, 450 g of portland cement produced by the Holderbank AG company, Rekingen, was mixed in a mixer according to the norms with 1350 g of standard sand (proportion of coarse:fine sand = 2:1) and 225 g of water which contained the copolymer as claimed in the invention in dissolved form. At a constant water/cement proportion of 0.50, the addition by doses of the products as claimed in the invention and the control products was done in such a way that the consistency of the mixtures remained comparable.
Immediately after production of the mortar, the slump and its temporal change were determined over a period of 90 minutes.
In addition, the setting behavior of the mortar mixtures with identical aonsistencies was determined.
The results of this comparative testing are abstracted in Table 1:
. : :
. -, , . -' :: , , .
21~68~
Table 1 Flow and setting behavior of mortar mixtures with copolymers as claimed in the invention and control mixtures.
Addi- Dose % Extent of slu~p Setting tive solid in mm after Beginn. End acc. matt.
to Ex. rel. to cement 0 m 15m 30m 45m 60m 75m 90m h:m h:m 1 0.17 202 185 176 171 164 159 152 8:00 9:30 2 0.20 203 186 178 170 163 158 150 7:55 9:20 3 0.20 196 190 178 169 162 154 148 7:30 9:00 4 0.20 208 191 179 ~72 167 160 154 8:00 9:25 0.20 190 180 175 170 163 157 151 7:15 8:45 6 0.30 196 191 187 179 175 170 164 7:20 8:45 7 0.16 202 188 182 172 166 160 150 7:50 9:20 8 0.17 203 183 174 170 164 160 148 7:50 9:20 9 O.Z0 208 195 187 176 170 166 159 8:00 9:20 0.20 195 185 177 169 164 160 156 7:25 9:00 11 0.175 lg6 183 178 171 168 162 157 7:35 9:05 12 0.175 202 192 186 181 171 167 164 8:20 9:50 13 0.175 202 188 175 171 162 156 148 7:00 8:30 14 0.20 206 198 lgl 184 180 174 168 8:30 10.00 V1 0.40 191 174 160 150 5:20 6:40 V2 0.40 190 168 146 5:30 7:00 V3 0.40 205 201 lg7 191 186 184 178 13:10 14:40 In order to describe the behavior of the products as claimed in the invention in their aqueous preparations during storage in comparison to conventional plasticisers for cement, some products were stored at a constant temperature of 60C over a period of 7 days and examined at certain intervals withiregard to their effectiveness:as a plasticiser for cement.
In Table 2j the extents of slump according to DIN 1164/7 after various storage periods are abstracted:
'.'' ' ' ' ' ' 211~88 Table 2:
Dispersing behavior of polymers as claimed in the invention and controls as a function of the period of storage of the aqueous preparations at 60C:
Additive acc. Dose % of Slump in mm after to Example solid matter 0 days 2 days 7 days rel. to cement 1 0.20 222 215 220 2 0.25 221 223 218 6 0.40 237 230 229 9 0.25 215 22~ 223 11 0.25 225 229 221 12 0.20 223 213 226 13 0.25 235 239 233 14 0.20 206 212 206 V4 0.20 227 220 197 ~. , : : , :. ,. : :
.: ,, . : . :: - ,~ : :
. . .. .
cyclohexylamine, 2-ethylhexylamine, n-laurylamine, glutamic acid, glycine, ~orpholine, sulphanilic acid, taurine, naph-thylaminesulphonic acid, naphthylaminedisulphonic acid, amino-ethanephosphonic acid and phosphanilic acid. Structural unit B
can also be present in the form of a corresponding semi-amide according to the formulas Bb and Bc.
The G monomers which produce structural element C are preferably compounds which possess a strong tendency to copolymerizate with maleic anhydrides. Examples of such monomers are: ethylene, propylene, n-butene, 2-methylpropene, diiso-2-methylpropene, cyclohexene, ~tyrene, alpha-methyl-styrene, indene, 4-methoxy~tyrene, 4-methylstyrene, ~inyl ace-tate, vinyl propionate, methylvinylether, ethylvinylether, isobutylvinylether, tetrahydrophthalic anhydride, n-butyl acrilate, methyl methacrylate, hydroxymethyl methacrylate or methacrylic acid.
These monomer~ or ~tr~ctural elements can, if necessary, al80 be employed in mixtures with one another or with other monomers.
A further object of the invention is a method for the production of copolymars characterized by the structural units : .
7 2~ 8 A to D which dispenses with the otherwise common organic : solvents, whereby a high yield of the copolymers are produced ~ with a method which is easy to use. For the production of the :: copolymers, a) one starts with a maleic acid semi-ester according to Formula E) or a mixture of a polyalkylene glycol monoether and maleic anhydride, which also reacts to the ~: maleic acid semi-ester according to Formula E at approximately 100 to 140C when an esterification catalyst is employed, or a mixture of maleic acid semi-ester, polyalkylene glycol monoether and maleic ~: anhydride, b) the monomer components according to Formula F or their ~ starting subs~ances, G and, if necessary, H, as well as .' more polyalkylene glycol monoethèr if necessary, as well .~ as common polymerization aids if necessary are added at . approximately 40 to 120C while being agitated, c) agitation of the mixture is continued at 40 to 150-C in :~ order to complete the polymerization reaction and the .~ polymer analogous conversion, and d) after cooling to approximately 50 to 80 C,.the reaction Z., mixture is normally neutralized with a base and diluted `.~ to the desired concentration with water.
.~
As claimed in the inventlon, either the polyalkylene glycol . monoether `required for the composition of the partial ~: structure A, or the macromer maleic acid semi-ester obtained in a previous reaction of maleic anhydride and the polyalkylene glycol monoether, or a mi~ture of both, may be .~ employed as a reaction medium. Preferably, the semi-e~ter i~
.. obtained at 120 - 140'C o~er a period of 2 to 4 hours, and -. preferably 0.5 to 1.0 w~ight ~ of an esterifying cataiyst such as ~ulphuric acid or toluene-p-sulphonic acid i.:employed. A~
claimed in the invention, a linear or branched alkoxypoly-`: alkylene glycol amine required for the composition of the partial structure B or .a mixture of polyalkylene glycol monoether and polyalkylene glycol amine monoether may be used . as a reaction medium.
.
, ..
,~;
., ,''~, ' .
8 ~ 6 8 ~
The bonding of structural elements A to D is preferably performed in such a way that one starts with a portion or all of the polyalkylene glycol monoether, which is mixed with a portion or all of the maleic anhydride. After completion of the previous reaction under the conditions described above, performed if necessary, the polymerization initiator is set and copolymerization is performed by adding the monomers which form structural units C, which can contain the polymerization initiator in a dissolved form if necessary. This inflow of monomers, however, can also contain the monomers which supply structural units B in the event that they are not miscible with one another. This method can, however, also be performed with 2 separate monomer inflows, preferably when the polymer analogous formation of structural element B
is impossible due to the insolubility of the amino compound in the polymer, such as when sulphanilic acid is employed.
Common additives such as those known to polymerization technology experts ~an be used as polymerization aids.
Preferably, these are polymerization initiators such as azo~isisobutyronitrile, azobis~2-methylvaleronotrile, dibenzo-yl peroxide, lauroyl peroxide, dicyclohexylpero20dicarbonate, tertiary butyl peroxy-2-ethylhexanoate and tertiary butyl perbenzoate, as well as polymerization accelerators or activators such as sodium bisulphitej ascorbic acid or salts from heavy metals, or molecular weight controllers such as dodecanethiol, tertiary dodecanethiol or diisopropylxanthogen disulphite.
Preferably, the polymerization reactions are performed at temperatures of approximately 40 to 120, more preferably at 60 to 100'C. The temperature~ for the subsequent reaction for completing the formation ~f esters, s~mi amide~, and/or imides are preferably 100 to 150-C.
In an especially preferred method of producing copolymers according to the invention, . ~ , . ..
~, 8a 2 1 1 4 6 ~ ~
a) one starts with a mixture of a polyalkylene glycol monoether of for-mula HO(CmH2mO)n R and a molar deficit of maleic anhydride, b) a mixture of a solution of an amine of formula NH2R or NHR2 in polyalkylene glycol monoether to which maleic anhy-dride is added while being agitated, a monomer component according to Formula G, if necessary by dbses from a separate inflow container, R
G) 13 l5 whereby M, R1, R2, R3, R~, R5, m and n have the meanings as described in Claim 1, as well as more polyalkylene glycol monoether if necessary, as well as common polymerization aids if necessary, are added at approximately 40 to 120-C while being agitated, c) the mixture is agitated further at 40 to 150'C to complete the polymerization reaction and the polymer ana-logous conversion, and d) the reaction mixture is normally neutralized with a base after cooling to approximately 50 to 80 C and diluted to the desired concentration with water.
i 211~68~
, ., `: ~
, .,~
When doing so, one starts with a partial amount of the polyalkylene glycol monoether required for the formation of structural element A together with a deficit of maleic anhydride. The monomer containing amino groups which is required for the composition of structural unit B, preferably ~-(4-sulphophenyl3maleic acid monoamide, is formed while being agitated in an agitable inflow container by dissolving 4-sulphanilic acid, which is preferably a salt, in the remaining amount of polyglycol and subsequently adding maleic anhydride.
The amount of initiator required for polymerization is also subsequently dissolved in this mixture. After the reactor receiver has been brought to polymerization temperature, the addition of the mixture is begun. At the same time, the addition of the monomers or monomer mixture required for the formation of structural element C from a separate inflow container is begun, and polymerization is conducted. After completion of polymerization, the polymer analogous esterification and , formation of amides or imides is completed at a higher temperature.
During polymerization, a vi~cous reaction ma~s is formed which is easily agitable a~d which is normally diluted with water after cooling to 50 - 80 C and neutralized by adding a ba~e, e.g.
an alk~line substance.
The method as claimed in the invention is characterized above all in that the yield is high, the residuai monomer propo* ion in the final product is low, and that it is simple, environ-mentally f~iendly, and safe.
lo 2 1 1 ~ 6 8 ~
All starting materials employed are components of the ~inal product, which is therefore free of undesirable solvent residues. At first, the polyalkylene glycol monoether serves as a reaction medium for the formation of certain monomers such as sulphophenyl maleic acid monoamide; later, it serves as a polymerization medium and has a positive effect on heat dissipation and agitability of the polymer. Finally, it is incorporated into the copolymer itself as a component via the free OH group. In contrast to known methods in which the production of carboxylic acid imide structures with substituents whlch carry sulphonic acid groups in polymers analogously to polymerization can be done only in an aqueous solution and under pressure and remains incomplete, the reaction is successful without pressure and produced a high yield with the aid of the method as claimed in the invention.
The copolymers as claimed in the invention are suitable as additives to aqueous suspensions of powdery substances such as clays, porcelain slips, silica flou~, chalk, carbon black, crushed rocks, pigments, talcum and plastic powders, though they are especially suitable for suspensions of hydraulic binders such as portland cement, portland blast-furnace cement, trass cement, fly-ash cement, aluminous cernent, magnesia cement, anhydrite or plaster in which they serve primarily as dispersing agents. Furthermore, the application or use of the ~opolymers as additives to hydraulic binders such as portland cement, portland blast-furnace cement, trass cement, fly-ash cement, anhydrite or plaster is preferable.
The copolymers as claimed in the invention can also be added to the hydraulic binders as a grinding aid for improving the grinding qualities, which means that the grinding process can be pl~nned mor!e efficiently.
.
The copolymers as claimed in the invention can be directly added to the cement mixtures such as cement masses, mortar or concrete in the form of their aqueous solutions or in anhydrous form in the amount of approximately O.O1 to 10 ~, preferably 0.05 to 3 ~ solid matter in relation to the weight --- 11 2114~8~
of the cement. Compared to the known additives, they demonstrate considerably increased dispersion, improved flow and setting qualities; they are free of formaldehyde and can maintain the flowability of the binder mixtures for a relatively long period of time. This means that the duration of processability of the binder mixtures can be increased with the aid of the copolymers as claimed in the invention due to the reduced slump loss. At the same time, however, the setting process of the finished building material is delayed only slightly. A further decisive advantage of the polymers according to the invention is that they do not lose their high initial ~ispersing power even after being stored for a relatively long period of time in the form of their aqueous preparations.
A further object of the invention are binder mixtures which contain hydraulic binders and the copolymers as claimed in the invention as well as water, common aggregates and additives, if necessary. A further object of the invention is a building material based on these binder mixtures.
A) Production ExamPles Example 1:
In a reaction container with a thermometer, agitator, ga~-entry tube, reflux condenser and 2 connections for separate inflow~, one starts with 282 g of methoxypolyethylene glycol (~oechst company) with a mean molecular weight (M) of 500 g/mole (0.564 mole) and mixes them with 6.1 g of maleic anhydride (0.062 mole) while agitating. The trapped air is replaced by ni!~rogen, and the contents of the flask are heated to 95 C.
At the same time, in a separate agitable inflow container (inflow 1) containing nitrogen, a solution of 282 g of methoxypolyethylene glycol (M ~ 500 g/mole, 0.564 mole) and 43.5 g of 4-sulphanilic acid-sodium salt dihydrate (0.188 .
:
12 ~ 8~
mole) is prepared, into which 122.8 g of maleic anhydride (1.253 mole) were introduced while agitating. When this was done, N-(4-sulphophenyl)maleic acid monoamide with an intense yellow coloration was obtained immediately, for which 15 mole % of the maleic anhydride employed was required.
Subsequently, 5.5 g of azobisisobutyronitrile (0.0335 mole) were added while being agitated, and this mixture was agitated until a completely clear solution was obtained. After the reaction temperature of 95C was reached in the polymerization container, the monomer solution which was prepared in the inflow container 1 and 137.1 g of styrene (1.318 mole) were added to the reactor from a second inflow container (inflow 2) by dose, continuously and simultaneously, over a period of 2 hours. After the addition process was complete, the mixture was agitated for another 2 hours at 95C, heated to 140C and agitated for a further 2 hours to complete esterification and the formation of imides.
The clear, orange-colored polymer melt was cooled to 50C
while being agitated and diluted by adding 130 g of distilled water. Subsequently, a pH value of 6.95 and a solid matter content of 36 weight ~ was achieved by adding 174 g of an a~ueous 20 % sodium hydroxide solution and 180 g of distilled water. A clear, yellowish-orange solution with a proportion of 0.39 weight ~ free styrene and a content of 0.17 weight maleic acid (determined by means of HPLC).
The mean molecular weight, determined by means of gel chromatography and using polyacrylic acid as a standard, amounted to 22,000 g/mole.
Example 2: I
The proce~ was similar to Example 1 with the difference that the inflows contained the following components:
nflow 1: 282.0 g methoxypolyethylene glycol (M=500 g/mole, 0.564 mole) ' 13 21146~
110.0 g malei,~ anhydride (1.122 mole) 3.1 g dodecanethiol 5.5 g azobisisobutyronitrile (0.0335 mole) Inflow 2: 125.5 g styrene (1.207 mole) 22.7 g N-phenylmaleimide (0.131 mole) After dilution and neutralization of the reddish-brown polymer melt, a clear, yellowish solution with a solid matter content of 33.9 weight %, 0.06 weight ~ non-converted styrene, 0.02 weight ~ free maleic acid and a mean molecular weight of the copolymer of 11,000 g/mole was obtained.
ExamPle 3:
Conversion as described in example 1 and 2 was repeated except that, instead of N-phenylmaleimide (Example 2), 26.3 g (0.131 mole) of N-(2,6-dimethylphenyl)maleimide, dissolved in 125.5 g of styrene, was employed. The final product, a clear, yellow aqueous solution, contained 34.4 weight % solid matter, 0.41 weight % free styrene and 0.17 weight % free maleic acid. The mean mol,scular weight amounted to 9,000 g/mole.
Example 4: ~
:- , Example 1 was repeated with the difference, however, that the N(4-sulphophenyl)maleic acid monoamide in inflow container 1 was employed as a preformed monomer in the form of a mononatrium salt in the amount of 35.7 g (0.122 mole). A
clear, yelIowish-orange copolymer solution with a solid matter co~tent of 36.0 weight ~, 0.2 weight ~ styr,sne, 0.07 weight ~
maleic acid and a mean molecular weight of 16,000 g/mole was obtained.
;
.~
.
~ . ..
- : ~:: - . :: -.
~ , ` 14 211~83 Example 5.
Copolymerization was repeated analogously to Example 1 with the following amounts and compositions of the inflows:
Inflow 1: 282.0 g methoxypolyethylene glycol (M=500 ~ g~mole, 0.564 mole) ; 122.8 g maleic anhydride (1.253 mole) 33.1 g 5-amino-2-naphthalenesulphonic acid-sodium salt (0.125 mole) 5.5 g azobisisobutyronitrile (0.0335 mole) Inflow 2: 137.1 g styrene (1.318 mole) The clear, deep brown polymer solution with a solid matter content of 35.9 weight % contained 0.22 weight ~ free styrene and 0.10 weight ~ free maleic acid at a mean molecular weight of 17,500 g/mole.
ExamPle 6:
Instead of 5-amino-2-naphthalenesulphonic acid-sodium salt as in Example 5, 43.6 g of 1-amino-3,6-naphthalenesulphonic acid-sodium salt (0.125 mole) was employed. The clear, blackish-brown polymer solution contained 35.5 weight ~ solid matter 0.37 weight % styrene and 0.21 weight ~ maleic acid and had a mean molecular weight of 19,500 g/mole.
Exam~le 7:
First, 600 g of methoxypol;yethylene glycol ~M = 500, 1.20 mole) were added to the same reaction container as described in Example 1 except with only one inflow connection, and 147 g of maleic anhydride (1.50 mole) were dissolved while being agitated. The trapped air was removed by rinsing with nitrogen, and the contents of the flask were heated to 95 C.
Subsequently, 156 g of styrene (1.50 mole) which contained t,~
21~8~
6.45 g of dissolved azobisisobutyronitrile (0.0393 mole) were added from an inflow container by uniform doses over a period of 2 hours, and the temperature was then held constant at 95~C
for a further 2 hours. Subsequently, a mixture of 11.1 g of butan-n-ol (0.15 mole) and 14.9 g of cyclohexylamine (0.15 mole) was added to the agitated reaction mass within 10 minutes, and the temperature was raised to 140C. After this temperature was reached, agitation was continued for another 2 hours at 140C to complete the formation of the esters and imides (analogous to polymerization), whereby a clear, deep orange polymer was obtained which was diluted with 1000 g of distilled water after cooling to 50C, adjusted to a pH value of 7.01 with 1~0 g of a 20 ~ sodium hydroxide solution at room temperature, and subsequently brought to a solid matter content of 36.1 weight ~ by adding a further 450 g of water.
The content of unconverted styrene was 0.58 weight ~; the free maleic acid content was 0.16 weight ~. The copolymer had a mean molecular weight of 23,000 g/mole.
ExamPle 8:
According to the method described in Example 7, except that instead of cyclohexylamine, 19.4 g (0.15 mole) of 2-ethylhexylamine were employed, and an aqueous copolymer solution with a solid matter content of 35.7 weight %, 0.22 weight ~ styrene, 0.22 weight % maleic acid and M=23,500 g/mole was obtained.
., .
Exam~le 9:
The method was analogous to Example 7, though with the followilhg changes:
.
Receiver: 500.0 g of methoxypolyethylene glycol (1.00 mole) 147.0 g of maleic anhydride (1.50 mole) .` :
'' ' : : ' -.". , -' : `
' 16 2i~46~
Before polymerization, the contents of the receiver were agitated for 1 hour at 130C
until partial esterification had taken place.
~nflow: 156.0 g styrene (1.50 mole) 6.45 g azobisisobutyronitrile (0.0393 mole) 3.6 g dodecanethiol After polymerization, imidization was performed by adding 24.5 g of cyclohexylamine (0.25 mole) and conducting a 2-hour conversion at 140C. The aqueous solution of the neutralized copolymer with a molecular weight of 2,500 g/mole was deep red and contained 37.0 weight % solid matter, 0.31 weight ~ free styrene and 0.03 weight % free maleic acid.
.
Example 10:
Example 9 was repeated with the difference that 32.3 g of 2-ethylhexylamine (0.25 mole) was employed instead of cyclohexamine. After processing, the copolymer with a mean molecular weight of 3,000 g/mole was present in the form of its sodium salt in an a~ueous solution with a solid matter content of 38.0 weight % and residual monomer proportions of 0.28 weight ~ styrene and 0.05 weight ~ maleic acid.
Exam~le 11:
Example 7 was repeated but with the following changes:
Receiver: 522 g methoxypolyethylene glycol (1.105 mole) 167 g ~ maleic anhydride (1.700 mole) Inflow: 221 g styrene (2.125 mole) 11.6 g dodecanethiol 9.7 g azobisisobutyronitrile 1.9 g azobiscyclohexanecarbonitrile ,~ ~ . . . ; . , : - . .
; . ~ i . - - : : ;
17 2~ 83 Polymerization was performed at lOSC with an inflow time of 60 minutes. After a subsequent reaction of 2 hours at 115C, 56.5 g of di-2-methoxyethylamine (0.425 mole) were added over a period of 15 minutes and agitated for 2 h at 140C to complete the ester and semi-amide formation. The crude product obtained was neutralized by adding water and Ca(OH)2.
., , ` Example 12:
The method was analogous to Example 11, although 28.3 g of di-2-methoxyethylamine were employed.
^ ExamPle 13:
Example 7 was repeated, but wlth the following changes:
.
Receiver: 600 g methoxypolyethylene-block-propylene glycol with a mean E0 value of 10 and 3 PO units (0.958 mole) 125 g maleic anhydride (1.278 mole) ;`
Inflow: 160 g styrene (1.534 mole~
8.6 g dodecanethiol 7.1 g azobisisobutyronitrile 1.4 g azobiscyclohexanecarbanitrile Polymerization was performed at 105-C. The inflow time amounted to 1 hour. After a subsequent reaction of 2 hours at 115-C, 17.0 g of di-2-methoxyethylamine (0.128 mole) were , added and agitated for another 2 hours at 140-C. A 40 %
.~ solution of ~he polymer was obtained Ly adding water and / calcium hydroxide.
' ' ' , ' ' ' . . , ~ , . . .
'j'': ~' ' ' ' ' ~' ~ ' ' ', 18 2tl~6~
Example 14:
Example 7 was repeated, but with the following changes:
Receiver: 455 g methoxypolyethylene glycol (0.910 mole) 137 g maleic anhydride (1.400 mole) Inflow: 182 g styrene (1.75 mole) 9.6 g dodecanethiol 8.0 g azobisisobutyronitrile 1.6 g azobiscyclohexanecarbonitrile Polymerization was performed at 105C (inflow time: 1 hour).
After a subsequent reaction of 120 minutes, 250 g of methoxypolyethylene glycol-block-propylene glycol amine with a mean EO value of 13 and a mean PO value of 3 units per mole were added over a period of 30 minutes. Afterwards, the reaction mixture was heated to 140C and agitated at 140C for 2 hours. Subsequently, the copolymer was cooled to lOO~C, diluted with water and neutralized with calcium hydroxide.
Control E~ample V1: -Commercial naphthalenesulphonic acid~formaldehyde polyconden-sate ("LIQUIMENT N" from Chemie Linz Ges.m.b.H.) Con~rol ExamPle V2:
Commercial melaminesulphonic acid-formaldehyde polycondensate ("LIQUIMENT MP-K" from Chemie Linz Ges.m.b.H.) , . ~
Control Exam~le V3:
According to the method described in the EP~A-402 563 tProduction Example 7), a copolymer was obtained from methoxy-polyethylene glycol monomaleate and N-vinyl pyrrolidone.
i . .
,= .
,, - : ~, 19 211~
Control ExamPle V4:
According to the method described in the EP-A-41 42 388 (Production Example 1), a copolymer was obtained from methoxypolyethylene glycol monomaleate and styrene.
B) APPlication E~mples The copolymers from examples 1 to 14 were subjected to comparative testing as a plasticiSer for cement mixtures in order to demonstrate their increased and longer lasting effectiveness in comparison to known plaSticisers According to DIN 1164/7, 450 g of portland cement produced by the Holderbank AG company, Rekingen, was mixed in a mixer according to the norms with 1350 g of standard sand (proportion of coarse:fine sand = 2:1) and 225 g of water which contained the copolymer as claimed in the invention in dissolved form. At a constant water/cement proportion of 0.50, the addition by doses of the products as claimed in the invention and the control products was done in such a way that the consistency of the mixtures remained comparable.
Immediately after production of the mortar, the slump and its temporal change were determined over a period of 90 minutes.
In addition, the setting behavior of the mortar mixtures with identical aonsistencies was determined.
The results of this comparative testing are abstracted in Table 1:
. : :
. -, , . -' :: , , .
21~68~
Table 1 Flow and setting behavior of mortar mixtures with copolymers as claimed in the invention and control mixtures.
Addi- Dose % Extent of slu~p Setting tive solid in mm after Beginn. End acc. matt.
to Ex. rel. to cement 0 m 15m 30m 45m 60m 75m 90m h:m h:m 1 0.17 202 185 176 171 164 159 152 8:00 9:30 2 0.20 203 186 178 170 163 158 150 7:55 9:20 3 0.20 196 190 178 169 162 154 148 7:30 9:00 4 0.20 208 191 179 ~72 167 160 154 8:00 9:25 0.20 190 180 175 170 163 157 151 7:15 8:45 6 0.30 196 191 187 179 175 170 164 7:20 8:45 7 0.16 202 188 182 172 166 160 150 7:50 9:20 8 0.17 203 183 174 170 164 160 148 7:50 9:20 9 O.Z0 208 195 187 176 170 166 159 8:00 9:20 0.20 195 185 177 169 164 160 156 7:25 9:00 11 0.175 lg6 183 178 171 168 162 157 7:35 9:05 12 0.175 202 192 186 181 171 167 164 8:20 9:50 13 0.175 202 188 175 171 162 156 148 7:00 8:30 14 0.20 206 198 lgl 184 180 174 168 8:30 10.00 V1 0.40 191 174 160 150 5:20 6:40 V2 0.40 190 168 146 5:30 7:00 V3 0.40 205 201 lg7 191 186 184 178 13:10 14:40 In order to describe the behavior of the products as claimed in the invention in their aqueous preparations during storage in comparison to conventional plasticisers for cement, some products were stored at a constant temperature of 60C over a period of 7 days and examined at certain intervals withiregard to their effectiveness:as a plasticiser for cement.
In Table 2j the extents of slump according to DIN 1164/7 after various storage periods are abstracted:
'.'' ' ' ' ' ' 211~88 Table 2:
Dispersing behavior of polymers as claimed in the invention and controls as a function of the period of storage of the aqueous preparations at 60C:
Additive acc. Dose % of Slump in mm after to Example solid matter 0 days 2 days 7 days rel. to cement 1 0.20 222 215 220 2 0.25 221 223 218 6 0.40 237 230 229 9 0.25 215 22~ 223 11 0.25 225 229 221 12 0.20 223 213 226 13 0.25 235 239 233 14 0.20 206 212 206 V4 0.20 227 220 197 ~. , : : , :. ,. : :
.: ,, . : . :: - ,~ : :
. . .. .
Claims (10)
1. Copolymers which are composed essentially of the structural elements A) B) a) b) and/or and/or c) C) and, if necessary, D) a) b) and/or whereby M: represents H or a cation such as alkaline or alkaline-earth metal, an ammonium group, or the residue of an organic amino group, R1: represents C1 to C20 alkyl, C5 to C8 cycloalkyl or aryl group residue, R2: represents H, C1 to C20 alkyl or hydroxyalkyl, C5 to C8 cycloalkyl or aryl group residue in which 1 or more H
atoms can be substituted by the structural elements -COOM, -SO3M and/or PO3M2, as well as structural units of the General Formula (CmH2mO)n R1, which can repeat if necessary, R3: represents H, a methyl or a methylene group which can be substituted if necessary and which forms a 5 to 8-member ring or an indene ring which includes R5, R4: represents H, a methyl or ethyl group, R5: represents H, C1 - C20 alkyl, C5 - C8 cycloalkyl or aryl group residue, which can be substituted if necessary, an alkoxy carbonyl group, an alkoxy group, an alkyl or aryl carboxylate group, a carboxylate group, a hydroxyalkoxy carbonyl group, m: represents a whole number from 2 to 4, n: represents a whole number from 0 - 100, preferably from 1 - 20.
atoms can be substituted by the structural elements -COOM, -SO3M and/or PO3M2, as well as structural units of the General Formula (CmH2mO)n R1, which can repeat if necessary, R3: represents H, a methyl or a methylene group which can be substituted if necessary and which forms a 5 to 8-member ring or an indene ring which includes R5, R4: represents H, a methyl or ethyl group, R5: represents H, C1 - C20 alkyl, C5 - C8 cycloalkyl or aryl group residue, which can be substituted if necessary, an alkoxy carbonyl group, an alkoxy group, an alkyl or aryl carboxylate group, a carboxylate group, a hydroxyalkoxy carbonyl group, m: represents a whole number from 2 to 4, n: represents a whole number from 0 - 100, preferably from 1 - 20.
2. Copolymers as claimed in Claim 1 characterized in that they are composed of 1 to 85 mole % structural element A, 1 to 85 mole % structural element B, 1 to 90 mole % structural element C, 0 to 50 mole % structural element D.
3. Copolymers as claimed in Claim 1 characterized in that they are composed of 20 to 55 mole % structural element A, 2 to 25 mole % structural element B, 40 to 60 mole % structural element C, 1 to 10 mole % structural element D.
4. A method for the production of copolymers as claimed in claim 1 characterized inthat a) one starts with a maleic acid semi-ester according to Formula E) or a mixture of a polyalkylene glycol monoether and maleic anhydride which also reacts to the maleic acid semi-ester according to Formula E at approximately 100 to 140°C when an esterification catalyst is employed, or one starts with a mixture of maleic acid semi-ester, polyalkylene glycol monoether and maleic anhydride, b) the monomer components according to Formula F) a) b) and/or and/or c) or their starting substances, G) and, if necessary, H) a) b) and/or whereby M, R1, R2, R3, R4, R5, m and n have the meanings as described in Claim 1, as well as more polyalkylene glycol monoether if necessary, as well as common polymerization aids if necessary, are added at approximately 40 to 120°C while being agitated, c) the mixture is agitated further at 40 to 150°C to complete the polymerization reaction and the polymer-analogous conversion, d) the reaction mixture is normally neutralized with a base after cooling to approximately 50 to 80°C and diluted to the desired concentration with water.
5. A method for the production of copolymers as claimed in Claim 1 characterized in that a) one starts with a mixture of a polyalkylene glycol monoether of for-mula HO(CmH2mO)n R1 and a molar deficit of maleic anhydride, b) a mixture of a solution of an amine of formula NH2R2 or NHR? in polyalkylene glycol monoether to which maleic anhy-dride is added while being agitated, a monomer component according to Formula G, if necessary by doses from a separate inflow container, G) whereby M, R1, R2, R3, R4, R5, m and n have the meanings as described in Claim 1, as well as more polyalkylene glycol monoether if necessary, as well as common polymerization aids if necessary, are added at approximately 40 to 120°C while being agitated, c) the mixture is agitated further at 40 to 150°C to complete the polymerization reaction and the polymer ana-logous conversion, and d) the reaction mixture is normally neutralized with a base after cooling to approximately 50 to 80°C and diluted to the desired concentration with water.
6. A method of using copolymers as claimed in claim 1 as additives to aqueous suspensions of inorganic or organic substances.
7. A method of using copolymers as claimed in claim 1 as additives to hydraulic binders.
8. A method for the improvement of the flow and setting characteristics and/or the grinding characteristics of hydrau-lic binders characterized in that copolymers as claimed in claim 1 are added to the hydraulic binders.
9. A binder mixture which contains hydraulic binders and copolymers as claimed in claim 1, as well as water, common aggregates and additives, if necessary.
10. A building material on the basis of a hydraulic binder which contains a copolymer as claimed in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0016293A AT399340B (en) | 1993-02-01 | 1993-02-01 | COPOLYMERS BASED ON MALEINIC ACID DERIVATIVES AND VINYL MONOMERS, THEIR PRODUCTION AND USE |
| ATA162/93 | 1993-02-01 | ||
| DE4304109A DE4304109A1 (en) | 1993-02-01 | 1993-02-11 | Copolymers based on maleic acid derivatives and vinyl monomers, their preparation and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2114688A1 true CA2114688A1 (en) | 1994-08-02 |
Family
ID=25591694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002114688A Abandoned CA2114688A1 (en) | 1993-02-01 | 1994-02-01 | Copolymers based on maleic acid derivatives and vinyl monomers, their production and application |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US5369198A (en) |
| EP (1) | EP0610699B1 (en) |
| JP (1) | JPH06322041A (en) |
| AT (2) | AT399340B (en) |
| AU (1) | AU672461B2 (en) |
| BR (1) | BR9400401A (en) |
| CA (1) | CA2114688A1 (en) |
| CZ (1) | CZ20494A3 (en) |
| DE (2) | DE4304109A1 (en) |
| DK (1) | DK0610699T3 (en) |
| ES (1) | ES2098066T3 (en) |
| FI (1) | FI940468A (en) |
| HU (1) | HUT67873A (en) |
| MA (1) | MA23100A1 (en) |
| NO (1) | NO302479B1 (en) |
| SI (1) | SI9400051A (en) |
| SK (1) | SK10294A3 (en) |
| ZA (1) | ZA94643B (en) |
Families Citing this family (68)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0628578A3 (en) * | 1993-06-11 | 1995-09-27 | Chemie Linz Gmbh | 2,6-Dimethylphenylphenymaleimide as comonomer in the copolymerisation of styrene or vinyl chlorid. |
| US5753744A (en) * | 1995-02-27 | 1998-05-19 | W.R. Grace & Co.-Conn. | Cement and cement composition having improved rheological properties |
| DE19513126A1 (en) * | 1995-04-07 | 1996-10-10 | Sueddeutsche Kalkstickstoff | Copolymers based on oxyalkylene glycol alkenyl ethers and unsaturated dicarboxylic acid derivatives |
| AU704079B2 (en) * | 1995-06-21 | 1999-04-15 | W.R. Grace & Co.-Conn. | Air controlling superplasticizers |
| US5703174A (en) * | 1995-06-21 | 1997-12-30 | W. R. Grace & Co.-Conn. | Air controlling superplasticizers |
| US5665158A (en) * | 1995-07-24 | 1997-09-09 | W. R. Grace & Co.-Conn. | Cement admixture product |
| GB9602084D0 (en) * | 1996-02-02 | 1996-04-03 | Sandoz Ltd | Improvements in or relating to organic compounds |
| GB9607570D0 (en) * | 1996-04-12 | 1996-06-12 | Sandoz Ltd | Improvements in or relating to organic compounds |
| DE69629030T2 (en) * | 1996-10-27 | 2004-04-22 | Sika Schweiz Ag | Dispersant for highly flowable, self-compacting concrete |
| US6384111B1 (en) * | 1996-12-20 | 2002-05-07 | Basf Aktiengesellschaft | Polymers containing carboxyl groups and polyalkylene ether side- chains as additives in mineral building materials |
| US6139623A (en) * | 1997-01-21 | 2000-10-31 | W. R. Grace & Co.-Conn. | Emulsified comb polymer and defoaming agent composition and method of making same |
| AT404730B (en) * | 1997-04-07 | 1999-02-25 | Holderchem Ag | ACRYLIC COPOLYMERS AND POLYMER COMPOSITIONS, AND THEIR USE AS ADDITIVES OR ADDITIVES FOR IMPROVING THE PROPERTIES OF DISPERSIONS AND BUILDING MATERIALS |
| RU2187479C2 (en) | 1997-06-25 | 2002-08-20 | В.Р. Грейс энд Ко.-Конн | Method for optimization of adding eo/po-type superplasticizer to smectite- containing concrete, and additive |
| US5985989A (en) * | 1997-07-09 | 1999-11-16 | Arco Chemical Technology, Lp | Method of making a water reducing additive for cement |
| DE19834173A1 (en) | 1997-08-01 | 1999-02-04 | Sueddeutsche Kalkstickstoff | Copolymer based on unsaturated di:carboxylic acid derivatives and oxyalkylene glycol-alkenyl ether(s) |
| FR2781806B1 (en) * | 1998-07-30 | 2000-10-13 | Rhodia Chimie Sa | WATER REDISPERSABLE POWDERS OF FILM-FORMING POLYMERS PREPARED FROM ETHYLENICALLY UNSATURATED MONOMERS |
| WO2000009460A1 (en) | 1998-08-14 | 2000-02-24 | Mbt Holding Ag | High pozzolan cement mixtures |
| WO2000009459A1 (en) | 1998-08-14 | 2000-02-24 | Mbt Holding Ag | Cementitious dry cast mixture |
| US6310143B1 (en) | 1998-12-16 | 2001-10-30 | Mbt Holding Ag | Derivatized polycarboxylate dispersants |
| JP3336456B2 (en) * | 1998-12-25 | 2002-10-21 | 日本シーカ株式会社 | Cement dispersant and concrete composition containing the dispersant |
| FR2815342B1 (en) | 2000-10-13 | 2003-08-01 | Francais Ciments | CEMENTITIOUS COMPOSITION, ITS USE FOR THE PRODUCTION OF A SELF-LEVELING LIQUID SCREW AND A SCREEN THUS OBTAINED |
| DE10060738A1 (en) | 2000-12-07 | 2002-06-27 | Skw Polymers Gmbh | Use of polycarboxylate-based flow agents for non-casein, casein-free or low-casein self-leveling putty and leveling compounds |
| DE10063291A1 (en) * | 2000-12-19 | 2002-06-20 | Skw Polymers Gmbh | Use of polycarboxylate-based plasticizers for anhydrite-based liquid screeds |
| JP4209685B2 (en) * | 2001-05-01 | 2009-01-14 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Antifoaming agent for water reducing agent admixture |
| CA2477709C (en) * | 2002-03-27 | 2011-02-01 | United States Gypsum Company | High molecular weight additives for calcined gypsum and cementitious compositions |
| US7338990B2 (en) * | 2002-03-27 | 2008-03-04 | United States Gypsum Company | High molecular weight additives for calcined gypsum and cementitious compositions |
| US20030230407A1 (en) * | 2002-06-13 | 2003-12-18 | Vijn Jan Pieter | Cementing subterranean zones using cement compositions containing biodegradable dispersants |
| EP1537058B1 (en) * | 2002-09-09 | 2008-06-04 | Construction Research & Technology GmbH | Fluidising composition |
| US20040226620A1 (en) | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
| US7053125B2 (en) * | 2002-11-14 | 2006-05-30 | The Board Of Trustees Of The University Of Illinois | Controlled dispersion of colloidal suspension by comb polymers |
| US6800129B2 (en) | 2003-01-30 | 2004-10-05 | W. R. Grace & Co.-Conn. | High solids pumpable cement additives |
| US7141617B2 (en) | 2003-06-17 | 2006-11-28 | The Board Of Trustees Of The University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
| CN101065338A (en) * | 2004-06-21 | 2007-10-31 | Sika技术股份公司 | Cement grinding aid |
| US7544242B2 (en) | 2005-06-14 | 2009-06-09 | United States Gypsum Company | Effective use of dispersants in wallboard containing foam |
| US8088218B2 (en) * | 2005-06-14 | 2012-01-03 | United States Gypsum Company | Foamed slurry and building panel made therefrom |
| US20060280899A1 (en) * | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Method of making a gypsum slurry with modifiers and dispersants |
| US7572328B2 (en) * | 2005-06-14 | 2009-08-11 | United States Gypsum Company | Fast drying gypsum products |
| US7875114B2 (en) * | 2005-06-14 | 2011-01-25 | United States Gypsum Company | Foamed slurry and building panel made therefrom |
| CA2607976A1 (en) * | 2005-06-14 | 2006-12-28 | United States Gypsum Company | Gypsum products utilizing a two-repeating unit dispersant and a method for making them |
| US20060280898A1 (en) * | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Modifiers for gypsum slurries and method of using them |
| US20060278127A1 (en) * | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Gypsum products utilizing a two-repeating unit dispersant and a method for making them |
| US20060278128A1 (en) * | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Effective use of dispersants in wallboard containing foam |
| US7504165B2 (en) * | 2005-06-14 | 2009-03-17 | United States Gypsum Company | High strength flooring compositions |
| JP4724843B2 (en) * | 2005-07-08 | 2011-07-13 | 東ソー株式会社 | Maleimide polymer |
| US7956102B2 (en) | 2007-04-09 | 2011-06-07 | The Board Of Trustees Of The University Of Illinois | Sol-gel inks |
| EP2090596A1 (en) * | 2008-02-13 | 2009-08-19 | Construction Research and Technology GmbH | Copolymer with polyether side chains and hydroxyalkyl and acid building blocks |
| DE102008021511A1 (en) * | 2008-04-30 | 2009-11-05 | Clariant International Limited | Pigment dispersants and easily dispersible solid pigment preparations |
| US8519029B2 (en) * | 2008-06-16 | 2013-08-27 | Construction Research & Technology Gmbh | Copolymer admixture system for workability retention of cementitious compositions |
| US7922939B2 (en) | 2008-10-03 | 2011-04-12 | The Board Of Trustees Of The University Of Illinois | Metal nanoparticle inks |
| US8187500B2 (en) | 2008-10-17 | 2012-05-29 | The Board Of Trustees Of The University Of Illinois | Biphasic inks |
| JP5673961B2 (en) | 2009-01-21 | 2015-02-18 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Robust polycarboxylates containing ether linkages for grinding preparation of cement materials |
| WO2010105979A1 (en) * | 2009-03-19 | 2010-09-23 | Henkel Ag & Co. Kgaa | Polymer-modified cement |
| KR101612725B1 (en) * | 2009-04-14 | 2016-04-15 | 라헤짜르 코미토프 | Maleimide-n-vinyllactam based sidechain polymers for lcd alignment layers |
| US8058377B1 (en) | 2010-06-24 | 2011-11-15 | W. R. Grace & Co.-Conn. | Phosphate-containing polycarboxylate polymer dispersants |
| EP2468698A1 (en) * | 2010-12-24 | 2012-06-27 | Sika Technology AG | Magnesia cement |
| JP5834923B2 (en) * | 2012-01-11 | 2015-12-24 | Dic株式会社 | Fiber sizing agent, coating agent and fiber material |
| JP6581575B2 (en) | 2013-10-18 | 2019-09-25 | ジーシーピー・アプライド・テクノロジーズ・インコーポレーテッド | System and method for achieving and monitoring fast response time of chemical fluidization admixture in hydratable concrete mix |
| DE102014210214A1 (en) | 2014-05-28 | 2015-12-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Use of oxyimide-containing copolymers or polymers as flame retardants, stabilizers, rheology modifiers for plastics, initiators for polymerization and grafting processes, crosslinking or coupling agents, and also plastic molding compositions containing such copolymers or polymers |
| US9919968B2 (en) | 2014-09-30 | 2018-03-20 | Gcp Applied Technologies Inc. | Low-to-mid-range water reduction using polycarboxylate comb polymers |
| CN106478855A (en) * | 2015-08-31 | 2017-03-08 | 华东理工大学 | A kind of bipolymer slurries additive agent of side chain graft benzenesulfonic acid base |
| JP2019515064A (en) * | 2016-04-26 | 2019-06-06 | ダウ グローバル テクノロジーズ エルエルシー | Clay Insensitive Concrete Superplasticizer |
| EP3549961A1 (en) | 2018-04-03 | 2019-10-09 | Evonik Röhm GmbH | Concrete flow improver and water reducing agent |
| DE102017213600A1 (en) | 2017-08-04 | 2019-02-07 | Evonik Röhm Gmbh | Concrete flow improvers |
| CN110997739B (en) | 2017-08-04 | 2022-12-16 | 罗姆化学有限责任公司 | Concrete flow improver and water reducer |
| DE102017213607A1 (en) | 2017-08-04 | 2019-02-07 | Evonik Röhm Gmbh | Flow improver and water reducer |
| US11021395B2 (en) | 2018-01-29 | 2021-06-01 | Lawrence L Kuo | Method for low-to-mid-range water reduction of cementitious compositions |
| US10538484B1 (en) * | 2018-09-12 | 2020-01-21 | China Petroleum & Chemical Corporation | Maleamic acid monomer and preparation method and use thereof |
| EP4203378A1 (en) | 2021-12-21 | 2023-06-28 | Basf Se | Apparatus for generating a digital access element associated with a polystyrene composition |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD71072A (en) * | ||||
| DE1182828B (en) * | 1960-12-02 | 1964-12-03 | Hoechst Ag | Process for the production of water-soluble copolymers |
| FR1371715A (en) * | 1963-10-19 | 1964-09-04 | Cement Marketing Company Ltd | New cement compositions and their preparations |
| US3563930A (en) * | 1968-04-01 | 1971-02-16 | Atlantic Richfield Co | Cement composition |
| US3544344A (en) * | 1968-04-18 | 1970-12-01 | Sinclair Research Inc | Set retarded plaster composition |
| US3923717A (en) * | 1974-08-19 | 1975-12-02 | Dow Chemical Co | A kiln feed slurry for making portland cement containing an inorganic slat of a styrene-maleic anhydride copolymer |
| GB1555521A (en) * | 1975-08-07 | 1979-11-14 | Crouzet P A | Composition for use as a concrete substitute |
| DD218699B1 (en) * | 1982-04-12 | 1989-07-26 | Wolfen Filmfab Veb | ELECTRIC PHOTOGRAPHIC FLUID DEVELOPER |
| US4478727A (en) * | 1982-09-13 | 1984-10-23 | Exxon Research & Engineering Co. | Sodium styrene sulfonate-co-sodium-n-(4-sulfophenyl)-maleimide- an improved viscosity control additive |
| EP0171189A3 (en) * | 1984-07-09 | 1986-12-30 | Texaco Development Corporation | Polymer composition and lubricating oil containing said composition as pour depressant |
| US4663386A (en) * | 1984-12-24 | 1987-05-05 | Atlantic Richfield Company | Flame-retardant molded composition which incorporates a poly(styrene-co-N-phenylmaleimide-co-dibromostyrene)copolymer |
| DE3530258A1 (en) * | 1985-08-23 | 1987-02-26 | Lentia Gmbh | USE OF SALTS OF WATER-SOLUBLE NAPHTALINE SULPHONIC ACID FORMALDEHYDE CONDENSATES AS ADDITIVES FOR INORGANIC BINDERS AND BUILDING MATERIAL |
| US4972025A (en) * | 1987-03-24 | 1990-11-20 | Nippon Shokubai Kagaku Kogyo, Co., Ltd. | Cement dispersant |
| DE3728786A1 (en) * | 1987-08-28 | 1989-03-09 | Sandoz Ag | Polymeric compounds, their preparation and use |
| DE3800091A1 (en) * | 1987-08-28 | 1989-07-13 | Sandoz Ag | COPOLYMERS, THEIR PRODUCTION AND USE |
| JPH0248453A (en) * | 1988-08-09 | 1990-02-19 | Nisso Masutaabirudaazu Kk | Production of quick-setting concrete for covering concrete |
| JP2676854B2 (en) * | 1988-12-16 | 1997-11-17 | 日本油脂株式会社 | Polyoxyalkylene unsaturated ether-maleic acid ester copolymer and use thereof |
| EP0402563B1 (en) * | 1989-05-17 | 1994-08-10 | Sika AG, vorm. Kaspar Winkler & Co. | Hydrosoluble polymers, process for their preparation and their use as dispersing agents in suspensions of solid materials |
| US5162060A (en) * | 1989-12-14 | 1992-11-10 | Rohm And Haas Company | Polymer-modified cements with improved chemical resistance |
| US5066709A (en) * | 1990-09-20 | 1991-11-19 | Gaf Chemicals Corporation | Bioadhesive composition |
| DE4135956C2 (en) * | 1990-11-06 | 2001-10-18 | Mbt Holding Ag Zuerich | Additive for cement mixtures and their use |
| CH682237A5 (en) * | 1990-12-29 | 1993-08-13 | Sandoz Ag | Styrene]-maleic acid half-ester copolymer, used as cement additive |
-
1993
- 1993-02-01 AT AT0016293A patent/AT399340B/en not_active IP Right Cessation
- 1993-02-11 DE DE4304109A patent/DE4304109A1/en not_active Withdrawn
-
1994
- 1994-01-21 DK DK94100854.2T patent/DK0610699T3/en active
- 1994-01-21 EP EP94100854A patent/EP0610699B1/en not_active Expired - Lifetime
- 1994-01-21 AT AT94100854T patent/ATE146489T1/en not_active IP Right Cessation
- 1994-01-21 DE DE59401289T patent/DE59401289D1/en not_active Expired - Fee Related
- 1994-01-21 ES ES94100854T patent/ES2098066T3/en not_active Expired - Lifetime
- 1994-01-27 MA MA23406A patent/MA23100A1/en unknown
- 1994-01-28 SK SK102-94A patent/SK10294A3/en unknown
- 1994-01-31 JP JP6009800A patent/JPH06322041A/en not_active Withdrawn
- 1994-01-31 HU HU9400270A patent/HUT67873A/en unknown
- 1994-01-31 NO NO940327A patent/NO302479B1/en unknown
- 1994-01-31 ZA ZA94643A patent/ZA94643B/en unknown
- 1994-01-31 CZ CZ94204A patent/CZ20494A3/en unknown
- 1994-01-31 AU AU54806/94A patent/AU672461B2/en not_active Ceased
- 1994-01-31 BR BR9400401A patent/BR9400401A/en not_active Application Discontinuation
- 1994-02-01 FI FI940468A patent/FI940468A/en unknown
- 1994-02-01 US US08/189,642 patent/US5369198A/en not_active Expired - Fee Related
- 1994-02-01 SI SI9400051A patent/SI9400051A/en unknown
- 1994-02-01 CA CA002114688A patent/CA2114688A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US5369198A (en) | 1994-11-29 |
| DE59401289D1 (en) | 1997-01-30 |
| ATE146489T1 (en) | 1997-01-15 |
| AU5480694A (en) | 1994-08-04 |
| HU9400270D0 (en) | 1994-05-30 |
| EP0610699B1 (en) | 1996-12-18 |
| NO940327L (en) | 1994-08-02 |
| NO302479B1 (en) | 1998-03-09 |
| MA23100A1 (en) | 1994-10-01 |
| AT399340B (en) | 1995-04-25 |
| SK10294A3 (en) | 1994-11-09 |
| FI940468A0 (en) | 1994-02-01 |
| DK0610699T3 (en) | 1997-01-06 |
| CZ20494A3 (en) | 1994-08-17 |
| ZA94643B (en) | 1994-09-19 |
| DE4304109A1 (en) | 1994-08-18 |
| AU672461B2 (en) | 1996-10-03 |
| SI9400051A (en) | 1994-09-30 |
| JPH06322041A (en) | 1994-11-22 |
| ES2098066T3 (en) | 1997-04-16 |
| BR9400401A (en) | 1994-08-23 |
| EP0610699A1 (en) | 1994-08-17 |
| FI940468A (en) | 1994-08-02 |
| HUT67873A (en) | 1995-05-29 |
| ATA16293A (en) | 1994-09-15 |
| NO940327D0 (en) | 1994-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2114688A1 (en) | Copolymers based on maleic acid derivatives and vinyl monomers, their production and application | |
| US6211317B1 (en) | Copolymers based on unsaturated dicarboxylic acid derivatives and oxyalkylene glycol alkenyl ethers | |
| JP3429410B2 (en) | Copolymer, method for producing the same, and additive for aqueous suspension comprising the same | |
| US5753744A (en) | Cement and cement composition having improved rheological properties | |
| AU2014213572B2 (en) | Copolymer admixture system for workability retention of cementitious compositions | |
| CA2554763C (en) | Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and oxyalkyleneglycol alkenyl ethers, method for the production thereof and use thereof | |
| US5665158A (en) | Cement admixture product | |
| US5583183A (en) | Cement and cement composition having improved rheological properties | |
| US5728207A (en) | Cement admixture product having improved rheological properties and process of forming same | |
| JP5156642B2 (en) | Copolymers based on unsaturated monocarboxylic or dicarboxylic acid derivatives and oxyalkylene glycol-alkenyl ethers, processes for their preparation and their use | |
| US20110166261A1 (en) | Dynamic Copolymers For Workability Retention of Cementitious Composition | |
| JP2000351820A (en) | Copolymer based on unsaturated monocarboxylic or dicarboxylic acid derivative radical and oxyalkylene glycol alkenyl ether radical, its production, and its use | |
| MX2007014246A (en) | Copolymers base on phosphorous-containing monomers, methods for the production thereof and their use. | |
| AU2014255949A1 (en) | Use of comb polymers for controlling the rheology of mineral binder compositions | |
| WO1996026976A1 (en) | Thermoplastic block copolymer with inherent anti-fog properties | |
| JPS61205653A (en) | Admixing agent for cement | |
| JPH07237953A (en) | Hydraulic composition and hydraulic composition molding | |
| JPH0515762A (en) | Dispersant composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |