CA1337005C - Copolymers of styrene and maleic acid anhydride/half ester - Google Patents
Copolymers of styrene and maleic acid anhydride/half esterInfo
- Publication number
- CA1337005C CA1337005C CA000575846A CA575846A CA1337005C CA 1337005 C CA1337005 C CA 1337005C CA 000575846 A CA000575846 A CA 000575846A CA 575846 A CA575846 A CA 575846A CA 1337005 C CA1337005 C CA 1337005C
- Authority
- CA
- Canada
- Prior art keywords
- formula
- ratio
- copolymers
- cementitious mixes
- cementitious
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
Abstract
The present invention discloses organic copolymers in free acid or salt form containing recurring units of formula I
I
in which R is an C2-6 alkylene radical, R1 is a C1-20 alkyl-, C6-9 cycloalkyl- or phenyl group, x,y and z are numbers from 0.01 to 100, m is a number from 1 to 100, n is a number from 10 to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-100. The organic copolymers are excellent surfactants and can also be used as additives in cementitious mixes.
I
in which R is an C2-6 alkylene radical, R1 is a C1-20 alkyl-, C6-9 cycloalkyl- or phenyl group, x,y and z are numbers from 0.01 to 100, m is a number from 1 to 100, n is a number from 10 to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-100. The organic copolymers are excellent surfactants and can also be used as additives in cementitious mixes.
Description
1 3370~5 Case 154-0122 ~OPOLYMERS OF STYRENE A~D MALEIC ACID ANHYDRIDE~ALF ESTER
This invention is concerned with new organic copolymers which can be used as additives to cementitious mixes.
More particularly, the invention relates to new organic copolymers in free acid or salt form containing recurring units of formula I
~ CH - CH ~ ( CH - CH ~ ~ H - CH
~ b Jx ~ o ~Y ~ OH O J Z
(R-0) - Rl ~ n in which R. .is an C2_6alkylene radical, Rl is a C1_20alkyl , C6_9cycloalkyl- or phenyl group, x, y and z are numbers from 0.01 to lO0, m is a number from l to lO0 and n is a number from lO to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-lO0.
It is clear to the man skilled in the art that all numbers given above are average values.
The organic copolymers of styrene and maleic acid anhydride/half ester preferably have an average molecular weight from 9.000 to lO0.000, more r'B ~
- - 2 - Case 154-0122 preferably from 12.000 to 36.000 and preferably have an even distribu-tion of styrene and maleic acid anhydride/half ester units, i.e. the ratio of x to (y~z) is from 1:3 to 3:1, most preferably the ratio of x to (y+z) is 1:1. Most preferred copolymers have an average molecular weight of about 18.000.
In formula I any alkyl or alkylene groups can be linear or branched and each R, independently, is preferably a C2_3alkylene group, most prefera-bly each R is the same and is ethylene. Each R1, independently, is pre-ferably Cl_2 alkyl, more preferably both groups R1 are methyl. m prefe-rably is a number from 7 to 20, most preferably 11-12. In order to have the necessary molecular weight, the copolymers of the invention contain at least 10, preferably from 18 to 40 structural units of formula I, i.e. n is preferably a number from 18 to 40. This means that the sum of m+n preferably is a number from 25 to 60. The acid groups of the copolymers with structural units of formula I can be in free acid or salt form. These salts can be alkali, alkaline earth, ammonium, alkylammonium or hydroxyammonium salts. Preferably these copolymers are in the form of alkali, especially sodium salts.
Organic copolymers with structural units of formula I can be produced by methods well known in the art, e.g. by reacting a copolymer having recurring units of formula II
CH - CH~\ (H--CH
C=O
with compounds of formula III
Rl - O -~R-O)~- H III
A
- 3 - Case 154-0122 and optionally reacting the resulting copolymer with an alkali or al-kaline earth base or with ammonia or with an alkylamino compound.
Depending on the amounts used the reaction of the maleic acid anhydride groups in the copolymer containing recurring units of formula II with the polyalkylene glycol of formula III can be substantially complete or incomplete, i.e. more or less anhydride groups will subsist in the final copolymer. A 100 ~ transformation which theoretically can be obtained with equimolar amounts of the reactants will, of course, never be achie-ved. Preferably almost all units of maleic anhydride in the copolymer of formula II are transformed into half ester units, i.e. the ratio of z:y should be as close to 100:1 as possible which can be controlled by de-termination of the acid number of the obtained copolymer.
Copolymers containing recurring units of formula II which are obtained by copolymerisation of styrene and maleic acid anhydride are well known and are described for example in C.E. Schildknecht, "Vinyl and related Polymers," John Uiley and Sons, Inc., New York, 1952.
Polyalkylene glycols of formula III are also well known compounds and are obtained by addition of alkylene oxides, especially ethylene oxide to alkyl- or cycloalkylalkohols or phenols.
The new copolymers with recurring units of formula I are excellent sur-factants and can be used to disperse organic and inorganic materials. In particular, they can be used as additives for cementitious mixes.
Cementitious mixes in which the organic copolymers of the invention canbe used as additives, are mortars and concretes. The hydraulic binder may be Portland cement, alumina cement or blended cement, for example pozzolanic cement, slag cement or other types, Portland cement being preferred.
The organic copolymers of the invention are added in amounts from 0.01 to 10 ~, preferably 0.1 to 3 ~ by weight based on the weight of the - 4 - Case 154-0122 cement. In such amounts, the organic copolymers of the invention have the property of fluidifying the cementitious mixes to which they have been added and are, therefore, excellent superplasticizers without having to the same extent the air entraining properties of similar copolymers with lower molecular weight.
Further admixtures conventional in cement technology, for example, set accelerators or retarders, frost protection agents, pigments, etc. may also be present in the cementitious mixes of the invention.
The following examples, in which all parts, ratios and percentages are by weight and all temperatures are expressed in degrees Centigrade, illustrate the invention.
E x a m p l e 49 Parts of maleic acid anhydride and 2.5 parts of n-dodecylmercaptan are dissolved in 200 parts of isobutylmethylketone and the solution heated to 110 under nitrogen while stirring. At this temperature a solution of l part azoisobutyronitrile in 52 parts styrene is added slowly over l hour. The reaction is slightly exothermic. The solvent is evaporated under vacuum (temperature in the solution being 50-55) and a pale yellow product is obtained, which is a copolymer having about 25 recurring units of formula 2 , CH -C=O ~C=O
and a molecular weight of about 5000 (determined by measurement of the viscosity, the intrinsic viscosity at 25 in acetone being 0,05 cm3/g).
35 Parts of this product are stirred together with 97 parts of the pro-duct with formula V
CH3 (OCH2CH2)12 - OH V
- 5 - Case 154-0122 under a nitrogen atmosphere at 180-190 over 2 hours, giving a brown oil with an acid number of 75-80 indicating complete reaction of the anhyd-ride groups. The molecular weight of the obtained product is about 18.000 (determined by measurement of the viscosity, the intrinsic vis-cosity at 25 in acetone being 0.15 cm3/g). The oil is dissolved in 306 parts of water and the solution brought to pH 6-7 by addition of caustic soda or triethanolamine. The resulting solution contains a polymer containing about 25 recurring units of formula ~CH - C~ - C~ CH - CH -J C=O C=O
0,05 ~3 ---t 2 2 )12 3 Na 63 E x a m p 1 e s 2 - 14 or NH --~CH2CH2H)3 , 0,95 Example 1 is repeated using the starting materials as listed in Table Iin which the compounds of formula VI, VII and VIII are CH3 (0CH2CH2~9 OH VI
CH3 ~0CH2CH2~7 OH VII
CH3- ~OCH2CH2)18 OH VIII
which can be prepared by reacting diethyleneglycolmonomethylether with ethylene oxide in appropriate amounts. The styrene - maleic acid anhyd-ride - copolymers are produced either in xylene or in isobutylmethyl-ketone.
- 6 - Case 154-0122 Application example A
0,3 % by weight of active substance (based on the weight of cement) of the copolymer of Example 1 is dissolved in 35 parts water and the solution is added to 100 parts Portland cement. The resulting mixture is kneaded by hand over 1 minute, after which the slump is determined as a function of time according to the method described in L.M. Meyer and W.F. Perenchio, Concrete International, 36-43, January 1979.
Application example A is repeated using instead of the product of Ex-ample 1 the amounts indicated in the last column of Table I of any one of the copolymers of Examples 2 to 14.
In comparison to a cementitious mix prepared under the same conditions with 0,3 % by weight of active substance based on the weight of cement, of a commercially available product which is a condensation product of naphthalenesulfonic acid and formaldehyde, the mixes prepared with the products of examples 1-14 have a better slump, especially when conside-ring the value of the slump as a function of time.
--o ~
c~ a~
w ~
o c L, O
C E ~ _ _ __ _ _ _ _ _ _ _ ~ OOOOOOOOOOOOO
E O Ul t~
' OOOOOOOOOOOOO
- V I o o o o o o o o oo o o o CJ .1 0 0 ~ 1 0 0Il-~ OO O O O
a~ b~ ~ . . . . . . . . .. . . .
~ O~`D ~ O O ~ OO O
a o c ~w m o H H
~ m ~ H H
~ E H H H
O 0~ Ll D D D D D D D D DD D D D
o W
_I m a, t~
v , - ~) aa~
.bO ~ Ll _I a~ Ll a) 3 ~ E O O O O O O O O OO O O O
L ~~ ~ g 0 81~1~ 1~ ~oo t~ a~ c ~ .. . . . . . .. . . . .
~ L~ O O ~O~
~ a u7 ~
~o ~ w ~
E~
a~
o e ~ u~ o u~
L~ -- C OO ~ ~ ~C'~C~C`~~`J
w o : o E3 ~ U~
a~ .- ~ ~ ~ ~ ~ ~ ~ ~
~ ~d a~
e X ~ ~ ~ U~ ~D r~ oo a~ o ~1 e~
This invention is concerned with new organic copolymers which can be used as additives to cementitious mixes.
More particularly, the invention relates to new organic copolymers in free acid or salt form containing recurring units of formula I
~ CH - CH ~ ( CH - CH ~ ~ H - CH
~ b Jx ~ o ~Y ~ OH O J Z
(R-0) - Rl ~ n in which R. .is an C2_6alkylene radical, Rl is a C1_20alkyl , C6_9cycloalkyl- or phenyl group, x, y and z are numbers from 0.01 to lO0, m is a number from l to lO0 and n is a number from lO to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-lO0.
It is clear to the man skilled in the art that all numbers given above are average values.
The organic copolymers of styrene and maleic acid anhydride/half ester preferably have an average molecular weight from 9.000 to lO0.000, more r'B ~
- - 2 - Case 154-0122 preferably from 12.000 to 36.000 and preferably have an even distribu-tion of styrene and maleic acid anhydride/half ester units, i.e. the ratio of x to (y~z) is from 1:3 to 3:1, most preferably the ratio of x to (y+z) is 1:1. Most preferred copolymers have an average molecular weight of about 18.000.
In formula I any alkyl or alkylene groups can be linear or branched and each R, independently, is preferably a C2_3alkylene group, most prefera-bly each R is the same and is ethylene. Each R1, independently, is pre-ferably Cl_2 alkyl, more preferably both groups R1 are methyl. m prefe-rably is a number from 7 to 20, most preferably 11-12. In order to have the necessary molecular weight, the copolymers of the invention contain at least 10, preferably from 18 to 40 structural units of formula I, i.e. n is preferably a number from 18 to 40. This means that the sum of m+n preferably is a number from 25 to 60. The acid groups of the copolymers with structural units of formula I can be in free acid or salt form. These salts can be alkali, alkaline earth, ammonium, alkylammonium or hydroxyammonium salts. Preferably these copolymers are in the form of alkali, especially sodium salts.
Organic copolymers with structural units of formula I can be produced by methods well known in the art, e.g. by reacting a copolymer having recurring units of formula II
CH - CH~\ (H--CH
C=O
with compounds of formula III
Rl - O -~R-O)~- H III
A
- 3 - Case 154-0122 and optionally reacting the resulting copolymer with an alkali or al-kaline earth base or with ammonia or with an alkylamino compound.
Depending on the amounts used the reaction of the maleic acid anhydride groups in the copolymer containing recurring units of formula II with the polyalkylene glycol of formula III can be substantially complete or incomplete, i.e. more or less anhydride groups will subsist in the final copolymer. A 100 ~ transformation which theoretically can be obtained with equimolar amounts of the reactants will, of course, never be achie-ved. Preferably almost all units of maleic anhydride in the copolymer of formula II are transformed into half ester units, i.e. the ratio of z:y should be as close to 100:1 as possible which can be controlled by de-termination of the acid number of the obtained copolymer.
Copolymers containing recurring units of formula II which are obtained by copolymerisation of styrene and maleic acid anhydride are well known and are described for example in C.E. Schildknecht, "Vinyl and related Polymers," John Uiley and Sons, Inc., New York, 1952.
Polyalkylene glycols of formula III are also well known compounds and are obtained by addition of alkylene oxides, especially ethylene oxide to alkyl- or cycloalkylalkohols or phenols.
The new copolymers with recurring units of formula I are excellent sur-factants and can be used to disperse organic and inorganic materials. In particular, they can be used as additives for cementitious mixes.
Cementitious mixes in which the organic copolymers of the invention canbe used as additives, are mortars and concretes. The hydraulic binder may be Portland cement, alumina cement or blended cement, for example pozzolanic cement, slag cement or other types, Portland cement being preferred.
The organic copolymers of the invention are added in amounts from 0.01 to 10 ~, preferably 0.1 to 3 ~ by weight based on the weight of the - 4 - Case 154-0122 cement. In such amounts, the organic copolymers of the invention have the property of fluidifying the cementitious mixes to which they have been added and are, therefore, excellent superplasticizers without having to the same extent the air entraining properties of similar copolymers with lower molecular weight.
Further admixtures conventional in cement technology, for example, set accelerators or retarders, frost protection agents, pigments, etc. may also be present in the cementitious mixes of the invention.
The following examples, in which all parts, ratios and percentages are by weight and all temperatures are expressed in degrees Centigrade, illustrate the invention.
E x a m p l e 49 Parts of maleic acid anhydride and 2.5 parts of n-dodecylmercaptan are dissolved in 200 parts of isobutylmethylketone and the solution heated to 110 under nitrogen while stirring. At this temperature a solution of l part azoisobutyronitrile in 52 parts styrene is added slowly over l hour. The reaction is slightly exothermic. The solvent is evaporated under vacuum (temperature in the solution being 50-55) and a pale yellow product is obtained, which is a copolymer having about 25 recurring units of formula 2 , CH -C=O ~C=O
and a molecular weight of about 5000 (determined by measurement of the viscosity, the intrinsic viscosity at 25 in acetone being 0,05 cm3/g).
35 Parts of this product are stirred together with 97 parts of the pro-duct with formula V
CH3 (OCH2CH2)12 - OH V
- 5 - Case 154-0122 under a nitrogen atmosphere at 180-190 over 2 hours, giving a brown oil with an acid number of 75-80 indicating complete reaction of the anhyd-ride groups. The molecular weight of the obtained product is about 18.000 (determined by measurement of the viscosity, the intrinsic vis-cosity at 25 in acetone being 0.15 cm3/g). The oil is dissolved in 306 parts of water and the solution brought to pH 6-7 by addition of caustic soda or triethanolamine. The resulting solution contains a polymer containing about 25 recurring units of formula ~CH - C~ - C~ CH - CH -J C=O C=O
0,05 ~3 ---t 2 2 )12 3 Na 63 E x a m p 1 e s 2 - 14 or NH --~CH2CH2H)3 , 0,95 Example 1 is repeated using the starting materials as listed in Table Iin which the compounds of formula VI, VII and VIII are CH3 (0CH2CH2~9 OH VI
CH3 ~0CH2CH2~7 OH VII
CH3- ~OCH2CH2)18 OH VIII
which can be prepared by reacting diethyleneglycolmonomethylether with ethylene oxide in appropriate amounts. The styrene - maleic acid anhyd-ride - copolymers are produced either in xylene or in isobutylmethyl-ketone.
- 6 - Case 154-0122 Application example A
0,3 % by weight of active substance (based on the weight of cement) of the copolymer of Example 1 is dissolved in 35 parts water and the solution is added to 100 parts Portland cement. The resulting mixture is kneaded by hand over 1 minute, after which the slump is determined as a function of time according to the method described in L.M. Meyer and W.F. Perenchio, Concrete International, 36-43, January 1979.
Application example A is repeated using instead of the product of Ex-ample 1 the amounts indicated in the last column of Table I of any one of the copolymers of Examples 2 to 14.
In comparison to a cementitious mix prepared under the same conditions with 0,3 % by weight of active substance based on the weight of cement, of a commercially available product which is a condensation product of naphthalenesulfonic acid and formaldehyde, the mixes prepared with the products of examples 1-14 have a better slump, especially when conside-ring the value of the slump as a function of time.
--o ~
c~ a~
w ~
o c L, O
C E ~ _ _ __ _ _ _ _ _ _ _ ~ OOOOOOOOOOOOO
E O Ul t~
' OOOOOOOOOOOOO
- V I o o o o o o o o oo o o o CJ .1 0 0 ~ 1 0 0Il-~ OO O O O
a~ b~ ~ . . . . . . . . .. . . .
~ O~`D ~ O O ~ OO O
a o c ~w m o H H
~ m ~ H H
~ E H H H
O 0~ Ll D D D D D D D D DD D D D
o W
_I m a, t~
v , - ~) aa~
.bO ~ Ll _I a~ Ll a) 3 ~ E O O O O O O O O OO O O O
L ~~ ~ g 0 81~1~ 1~ ~oo t~ a~ c ~ .. . . . . . .. . . . .
~ L~ O O ~O~
~ a u7 ~
~o ~ w ~
E~
a~
o e ~ u~ o u~
L~ -- C OO ~ ~ ~C'~C~C`~~`J
w o : o E3 ~ U~
a~ .- ~ ~ ~ ~ ~ ~ ~ ~
~ ~d a~
e X ~ ~ ~ U~ ~D r~ oo a~ o ~1 e~
Claims (9)
1. A process for the improvement of the fluidity of cementitious mixes comprising an hydraulic binder, aggregate and water, comprising adding an organic copolymer with recurring units of formula I
(I) in which R is an C2-6 alkylene radical, R1 is a C1-20 alkyl, C6-9 cycloalkyl or phenyl group, x,y and z are numbers from 0.01 to 100, m is a number from 7 to 20, n is a number from 10 to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-100.
(I) in which R is an C2-6 alkylene radical, R1 is a C1-20 alkyl, C6-9 cycloalkyl or phenyl group, x,y and z are numbers from 0.01 to 100, m is a number from 7 to 20, n is a number from 10 to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-100.
2. Cementitious mixes comprising a cementitious product and a copolymer in free acid or salt form containing recurring units of formula I
in which R is an alkylene radical with 2 to 6 carbon atoms, R1 is a C1-20 alkyl, C6-9 cycloalkyl or phenyl group, x,y and z are numbers from 0.01 to 100, m is a number from 7 to 20, n is a number from 10 to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-100.
in which R is an alkylene radical with 2 to 6 carbon atoms, R1 is a C1-20 alkyl, C6-9 cycloalkyl or phenyl group, x,y and z are numbers from 0.01 to 100, m is a number from 7 to 20, n is a number from 10 to 100, with the provisos, that i) the ratio of x to (y+z) is from 1:10 to 10:1 inclusive, ii) the ratio of z:y is from 3:1 to 100:1, and iii) m + n = 15-100.
3. Cementitious mixes according to claim 2. in which the organic copolymer has an average molecular weight from 9,000 to 100,000.
4. Cementitious mixes according to claim 3, in which the organic copolymer has an average molecular weight from 12,000 to 36,000.
5. Cementitious mixes according to claim 2, in which the ratio of x to (y+z) is from 1:3 to 3:1.
6. Cementitious mixes according to claim 2, in which in formula I R is an alkylene radical with 2 or 3 carbon atoms.
7. Cementitious mixes according to claim 2, in which in formula I R1 is a C1-2 alkylene group.
8. Cementitious mixes according to claim 2, in which in formula I n is a number from 18-40.
9. Cementitious mixes according to claim 2, in which the organic copolymer contains recurring units of formula I in which R is an ethylene group, R1 is methyl, the ratio of x to (y+z) is 1:1, m is a number 11-12 and n is a number 18-25.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873728786 DE3728786A1 (en) | 1987-08-28 | 1987-08-28 | Polymeric compounds, their preparation and use |
| DEP3728786.9 | 1987-08-28 | ||
| DE3800091A DE3800091A1 (en) | 1987-08-28 | 1988-01-05 | COPOLYMERS, THEIR PRODUCTION AND USE |
| DEP3800091.1 | 1988-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1337005C true CA1337005C (en) | 1995-09-12 |
Family
ID=25859136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000575846A Expired - Fee Related CA1337005C (en) | 1987-08-28 | 1988-08-26 | Copolymers of styrene and maleic acid anhydride/half ester |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5158996A (en) |
| EP (1) | EP0306449B1 (en) |
| JP (1) | JPH0759613B2 (en) |
| AU (1) | AU607534B2 (en) |
| CA (1) | CA1337005C (en) |
| DE (2) | DE3800091A1 (en) |
| ES (1) | ES2051889T3 (en) |
| FI (1) | FI883950A (en) |
| HK (1) | HK132297A (en) |
Families Citing this family (79)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN172215B (en) * | 1987-03-25 | 1993-05-08 | Lubrizol Corp | |
| 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 |
| US5612396A (en) * | 1990-12-29 | 1997-03-18 | Sandoz Ltd. | Copolymers |
| CH686780A5 (en) * | 1992-07-22 | 1996-06-28 | Sandoz Ag | Fliessfaehige cement mixtures. |
| AT399340B (en) * | 1993-02-01 | 1995-04-25 | Chemie Linz Gmbh | COPOLYMERS BASED ON MALEINIC ACID DERIVATIVES AND VINYL MONOMERS, THEIR PRODUCTION AND USE |
| EP0641746B1 (en) * | 1993-09-08 | 2002-11-06 | Mbt Holding Ag | Cementitious compositions for layered applications |
| IT1279390B1 (en) * | 1993-12-21 | 1997-12-10 | Sandoz Ag | ADDITIONAL COPOLYMERS USEFUL AS FLUIDIFYING ADDITIVES FOR CEMENTITIOUS MIXTURES |
| DE4421722A1 (en) * | 1994-06-21 | 1996-01-04 | Sueddeutsche Kalkstickstoff | Flow improver for cement binders, esp. self-levelling materials |
| US5576145A (en) * | 1995-02-10 | 1996-11-19 | Morton International, Inc. | Esterified styrene/maleic anhydride polymer and polymer-containing photoimageable composition having improved alkaline process resistance |
| AU4907296A (en) * | 1995-02-27 | 1996-09-18 | W.R. Grace & Co.-Conn. | Thermoplastic block copolymer with inherent anti-fog properties |
| US5753744A (en) * | 1995-02-27 | 1998-05-19 | W.R. Grace & Co.-Conn. | Cement and cement composition having improved rheological properties |
| DE69633329T2 (en) * | 1995-03-06 | 2005-09-15 | W.R. Grace & Co.-Conn. | CEMENT COMPOSITIONS |
| GB9505259D0 (en) * | 1995-03-16 | 1995-05-03 | 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 |
| 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 |
| DE69839176T2 (en) * | 1997-05-15 | 2009-03-26 | Construction Research & Technology Gmbh | CEMENT COMPOSITION HIGHLY CONTAINING PUZZANINE-REPLACED CEMENT AND COMPATIBLE MIXTURES FOR IT |
| US6136950A (en) * | 1997-09-23 | 2000-10-24 | Mbt Holding Ag | Highly efficient cement dispersants |
| EP0930395A1 (en) * | 1998-01-20 | 1999-07-21 | Dow Europe S.A. | Low foaming paper surface sizing composition |
| EP0930321A1 (en) * | 1998-01-20 | 1999-07-21 | Dow Europe S.A. | Intrinsically low foaming copolymers and their use as cement additives |
| US6075093A (en) | 1998-03-24 | 2000-06-13 | National Starch And Chemical Investment Holding Corporation | Laundry detergents containing styrene-anhydride copolymers grafted with polyethylene glycol |
| AU2122599A (en) * | 1998-03-24 | 1999-10-07 | National Starch And Chemical Investment Holding Corporation | Laundry detergents containing styrene-anhydride copolymers grafted with polyethylene glycol |
| ES2211157T3 (en) | 1998-08-14 | 2004-07-01 | CONSTRUCTION RESEARCH & TECHNOLOGY GMBH | CEMENT MIXED DRY MOLDED. |
| DK1044175T3 (en) | 1998-08-14 | 2003-03-17 | Mbt Holding Ag | Cement mixtures with high pozzolan content |
| GB2340521B (en) * | 1998-08-15 | 2000-09-13 | Sofitech Nv | Shale-stabilizing additives |
| EP0985691A1 (en) * | 1998-09-10 | 2000-03-15 | Dow Deutschland Inc., Zweigniederlassung Stade | Process for preparing hydrophobically modified low foaming copolymers, hydrophobically modified low foaming copolymers and their use as cement additives |
| DE19842859A1 (en) | 1998-09-18 | 2000-03-23 | Basf Ag | Mixture of polycarboxylate-based liquefier and deaerating agent for cement-based building materials, e.g. concrete, contains butoxylated polyalkylene-polyamine or salts as a deaerating agent |
| US6310143B1 (en) * | 1998-12-16 | 2001-10-30 | Mbt Holding Ag | Derivatized polycarboxylate dispersants |
| CN1113046C (en) * | 1998-12-28 | 2003-07-02 | 株式会社日本触媒 | Cement additire, cement composition and polycarboxylic acid polymer |
| JP4502421B2 (en) * | 1999-05-13 | 2010-07-14 | 株式会社日本触媒 | Cement additive and cement composition |
| US6861459B2 (en) * | 1999-07-09 | 2005-03-01 | Construction Research & Technology Gmbh | Oligomeric dispersant |
| US6528593B1 (en) | 1999-09-10 | 2003-03-04 | The Dow Chemical Company | Preparing copolymers of carboxylic acid, aromatic vinyl compound and hydrophobic polyalkylene oxide |
| EP1242330B1 (en) | 1999-12-10 | 2005-06-29 | Construction Research & Technology GmbH | Solubilized defoamers for cementitious compositions |
| JP2003516300A (en) | 1999-12-10 | 2003-05-13 | エムビーティー ホールディング アーゲー | Water-soluble air control agent for cementitious composition |
| US6875801B2 (en) * | 1999-12-10 | 2005-04-05 | Construction Research & Technology Gmbh | Solubilized defoamers for cementitious compositions |
| US8088842B2 (en) * | 1999-12-10 | 2012-01-03 | Construction Research & Technology Gmbh | Solubilized defoamers for cementitious compositions |
| US20030187100A1 (en) * | 1999-12-10 | 2003-10-02 | Mbt Holding Ag | Water soluble air controlling agents for cementitious compositions |
| JP3725414B2 (en) * | 2000-10-06 | 2005-12-14 | 竹本油脂株式会社 | Air amount stabilizer for hydraulic cement composition and hydraulic cement composition |
| US6642320B2 (en) * | 2001-07-02 | 2003-11-04 | Taiheiyo Cement Kabushiki Kaisha | Multi-functional cement dispersants and hydraulic cement compositions |
| US6858074B2 (en) * | 2001-11-05 | 2005-02-22 | Construction Research & Technology Gmbh | High early-strength cementitious composition |
| US20030230407A1 (en) * | 2002-06-13 | 2003-12-18 | Vijn Jan Pieter | Cementing subterranean zones using cement compositions containing biodegradable dispersants |
| DE10237286A1 (en) | 2002-08-14 | 2004-02-26 | Degussa Construction Chemicals Gmbh | Use of block copolymers produced by polymerizing a polyalkylene oxide compound with an ethylenically unsaturated monomer as dispersants for aqueous suspensions, e.g. cement mixes |
| US20040149174A1 (en) * | 2003-02-05 | 2004-08-05 | Mbt Holding Ag | Accelerating admixture for concrete |
| EP1603846B1 (en) | 2003-02-26 | 2012-07-11 | Construction Research & Technology GmbH | Strength improvement admixture |
| MXPA05010352A (en) | 2003-03-27 | 2006-03-08 | Constr Res & Tech Gmbh | Liquid coloring suspension. |
| US20040211342A1 (en) * | 2003-04-25 | 2004-10-28 | Mbt Holding Ag | Rheology stabilizer for cementitious compositions |
| US7556684B2 (en) * | 2004-02-26 | 2009-07-07 | Construction Research & Technology Gmbh | Amine containing strength improvement admixture |
| KR20070026594A (en) | 2004-06-15 | 2007-03-08 | 컨스트럭션 리서치 앤 테크놀로지 게엠베하 | Providing freezing and thawing resistance to cementitious compositions |
| NZ562556A (en) | 2005-06-14 | 2011-03-31 | Constr Res & Tech Gmbh | Providing freezing and thawing resistance to cementitious compositions |
| DE102005061153A1 (en) * | 2005-12-21 | 2007-06-28 | Construction Research & Technology Gmbh | New copolymers for use as additive in aqueous suspension of mineral or bituminous binder e.g. cement, lime or gypsum or dispersion binder powder comprise unsaturated mono- or dicarboxylic acid derivative and oxyalkylene glycol alkenyl ether |
| US7815731B2 (en) | 2006-06-13 | 2010-10-19 | Sekisui Specialty Chemicals America, Llc | Polyvinyl alcohol fluid loss additive with improved rheological properties |
| CN101778805A (en) | 2007-08-10 | 2010-07-14 | 建筑研究和技术有限公司 | Rheology modifying additive for dry cast cementitious compositions |
| US7973110B2 (en) | 2008-06-16 | 2011-07-05 | Construction Research & Technology Gmbh | Copolymer synthesis process |
| CN108947375B (en) | 2008-09-02 | 2022-02-22 | 建筑研究和技术有限公司 | Hardening accelerator composition comprising a plasticizer |
| JP2013503926A (en) | 2009-09-02 | 2013-02-04 | ビーエーエスエフ コンストラクション ポリマース ゲゼルシャフト ミット ベシュレンクテル ハフツング | Formulation and use thereof |
| PE20121415A1 (en) * | 2009-09-02 | 2012-11-17 | Constr Res & Tech Gmbh | SPRAYABLE HYDRAULIC BINDER COMPOSITION |
| US20110054081A1 (en) | 2009-09-02 | 2011-03-03 | Frank Dierschke | Formulation and its use |
| WO2011026720A1 (en) | 2009-09-02 | 2011-03-10 | Construction Research & Technology Gmbh | Hardening accelerator composition containing phosphated polycondensates |
| EP2473459A1 (en) | 2009-09-02 | 2012-07-11 | Construction Research & Technology GmbH | Sulphonic acid and aromatic groups containing hardening accelerator compositions |
| DE102011089535A1 (en) | 2011-12-22 | 2013-06-27 | Evonik Industries Ag | Defoamer compositions for building material mixtures |
| US8845940B2 (en) | 2012-10-25 | 2014-09-30 | Carboncure Technologies Inc. | Carbon dioxide treatment of concrete upstream from product mold |
| JP6381551B2 (en) | 2013-01-25 | 2018-08-29 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Curing accelerator composition |
| US20140216303A1 (en) | 2013-02-04 | 2014-08-07 | Michael Lee | System and method of applying carbon dioxide during the production of concrete |
| US20160107939A1 (en) | 2014-04-09 | 2016-04-21 | Carboncure Technologies Inc. | Methods and compositions for concrete production |
| US9376345B2 (en) | 2013-06-25 | 2016-06-28 | Carboncure Technologies Inc. | Methods for delivery of carbon dioxide to a flowable concrete mix |
| US10927042B2 (en) | 2013-06-25 | 2021-02-23 | Carboncure Technologies, Inc. | Methods and compositions for concrete production |
| US9108883B2 (en) | 2013-06-25 | 2015-08-18 | Carboncure Technologies, Inc. | Apparatus for carbonation of a cement mix |
| US9388072B2 (en) | 2013-06-25 | 2016-07-12 | Carboncure Technologies Inc. | Methods and compositions for concrete production |
| EP2842921A1 (en) | 2013-08-27 | 2015-03-04 | Construction Research & Technology GmbH | Novel fibers, methods for their preparation and use in the manufacture of reinforced elements |
| EP2842927A1 (en) | 2013-08-29 | 2015-03-04 | BASF Construction Polymers GmbH | Hardening accelerator containing ettringite and calcium silicate hydrate |
| WO2015123769A1 (en) | 2014-02-18 | 2015-08-27 | Carboncure Technologies, Inc. | Carbonation of cement mixes |
| CA2943791C (en) | 2014-04-07 | 2023-09-05 | Carboncure Technologies Inc. | Integrated carbon dioxide capture |
| CA2977417A1 (en) | 2015-02-27 | 2016-09-01 | Basf Se | Use of csh-seed modified fibers in oil field applications |
| SG11201810010PA (en) | 2016-04-11 | 2018-12-28 | Carboncure Tech Inc | Methods and compositions for treatment of concrete wash water |
| EP3448825B1 (en) * | 2016-04-26 | 2020-05-27 | Dow Global Technologies LLC | Cementitious composition comprising a clay insensitive concrete superplasticizer |
| CA3119769A1 (en) | 2018-11-20 | 2020-05-28 | The Lubrizol Corporation | Graphene production and composition |
| CN109666148A (en) * | 2018-12-29 | 2019-04-23 | 东来涂料技术（上海）股份有限公司 | A kind of preparation method of aqueous dispersion |
| US20230107433A1 (en) | 2020-02-27 | 2023-04-06 | Basf Se | Uncharged clay blocking agent |
| JP6993605B1 (en) * | 2021-03-31 | 2022-02-04 | 千住金属工業株式会社 | Flux and solder paste |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3207718A (en) * | 1961-03-23 | 1965-09-21 | Dow Chemical Co | Epoxy modified vinyl copolymers of alpha, beta-unsaturated dicarboxylic acid partialesters |
| US3311584A (en) * | 1964-03-02 | 1967-03-28 | Dow Chemical Co | Interpolymers of vinylidene aromatic, butadiene and half ester of maleic acid |
| 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 |
| JPS5325049B2 (en) * | 1972-11-15 | 1978-07-25 | ||
| JPS5898305A (en) * | 1981-12-07 | 1983-06-11 | Sumitomo Chem Co Ltd | Production of decolorized styrene/maleic acid low polymer |
| JPS59139396A (en) * | 1983-01-31 | 1984-08-10 | Kuraray Co Ltd | Neocarzinostatin complex and its preparation |
| JPS59115315A (en) * | 1982-12-21 | 1984-07-03 | Idemitsu Kosan Co Ltd | Production of copolymer |
| JPS60120711A (en) * | 1983-12-05 | 1985-06-28 | Dainippon Ink & Chem Inc | Synthetic coating resin and its production |
| DE3404537A1 (en) * | 1984-02-09 | 1985-08-14 | Hoechst Ag, 6230 Frankfurt | AQUEOUS FUNCTIONAL LIQUIDS BASED ON POLYMERS |
| JPS60260461A (en) * | 1984-06-04 | 1985-12-23 | 大倉工業株式会社 | Manufacture of polymer cement composite body reinforced withmetal network |
| US4655838A (en) * | 1984-09-27 | 1987-04-07 | Idemitsu Petrochemical Co., Ltd. | Cement additive composition |
| US4616074A (en) * | 1985-10-01 | 1986-10-07 | Alco Chemical Corporation | Acrylic-methylene succinic ester emulsion copolymers for thickening aqueous systems |
-
1988
- 1988-01-05 DE DE3800091A patent/DE3800091A1/en not_active Withdrawn
- 1988-08-22 EP EP88810573A patent/EP0306449B1/en not_active Expired - Lifetime
- 1988-08-22 ES ES88810573T patent/ES2051889T3/en not_active Expired - Lifetime
- 1988-08-22 DE DE88810573T patent/DE3888054D1/en not_active Expired - Lifetime
- 1988-08-26 JP JP63210841A patent/JPH0759613B2/en not_active Expired - Fee Related
- 1988-08-26 CA CA000575846A patent/CA1337005C/en not_active Expired - Fee Related
- 1988-08-26 FI FI883950A patent/FI883950A/en not_active IP Right Cessation
- 1988-08-26 AU AU21585/88A patent/AU607534B2/en not_active Ceased
-
1990
- 1990-09-27 US US07/589,345 patent/US5158996A/en not_active Expired - Fee Related
-
1997
- 1997-06-26 HK HK132297A patent/HK132297A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3888054D1 (en) | 1994-04-07 |
| EP0306449A2 (en) | 1989-03-08 |
| AU607534B2 (en) | 1991-03-07 |
| ES2051889T3 (en) | 1994-07-01 |
| EP0306449B1 (en) | 1994-03-02 |
| FI883950A (en) | 1989-03-01 |
| EP0306449A3 (en) | 1989-05-17 |
| US5158996A (en) | 1992-10-27 |
| AU2158588A (en) | 1989-03-02 |
| FI883950A0 (en) | 1988-08-26 |
| HK132297A (en) | 1997-10-03 |
| JPH0192212A (en) | 1989-04-11 |
| DE3800091A1 (en) | 1989-07-13 |
| JPH0759613B2 (en) | 1995-06-28 |
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