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US 5,476,885 AGranted
Cement additive, method for producing the same, and cement composition
AssigneeNippon Shokubai Co., Ltd.
InventorsHideyuki Tahara, Hiroshi Ito, Yasuhiro Mori, Makoto Mizushima
Life of this patent
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Abstract
A cement additive composed of a crosslinked polymer in which, between main chains having a water-soluble polymer structure of a molecular weight from 500 to 100,000, there is a bond having as a structural unit at least one divalent group having the following formula (I): ##STR1## where R.sup.1 and R.sup.2 independently denote any one of the following: ##STR2## where R.sup.1 is not required, if R.sup.2 is the following: ##STR3## and where R and R' independently denote an alkyl group of carbon number of 1 to 5.
Claims28
A cement additive comprising a crosslinked polymer in which, between main chains having a water-soluble polymer structure of a weight average molecular weight from 500 to 100,000, a bond having as a structural unit at least one divalent group having the following formula (I) is formed ##STR29## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR30## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR31## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5, said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein said main chains comprise at least one member selected from the group consisting of ##STR32## wherein m is 0 or an integral number of 1 to 50;
- n is 0 or 1;
- M is at least one member selected from the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group and an organic amine group;
- R.sup.5 and R.sup.6 independently denote an alkylene group of carbon number 2 to 4;
- R.sup.7 denotes an alkylene group of carbon number 1 to 5;
- with the proviso that when m is at least 2, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular;
- and wherein said main chains further comprise at least one functional group selected from the group consisting of ##STR33## wherein p is an integral number of 1 to 10;
- q is 0 or an integral number of 1 to 100;
- r and s are, respectively, an integral number of 1 to 3;
- t and u are, respectively, an integral number of 1 to 100;
- A.sup.1 is a straight chain divalent or branched trivalent ring-opened group of an alkyleneimine of 2 to 4 carbon atoms;
- R.sup.8 denotes CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.9 denotes H, CH.sub.3, or C.sub.2 H.sub.5 ;
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5;
- and
- X.sup..crclbar. denotes an anionic pair ion,
- with the proviso that, when p is at least two, a plurality of A.sup.1 groups may be the same or different and, when a plurality of A.sup.1 are different from one another, their arrangement may be regular or irregular;
- and with the provision that when q is an integral number of from 1-100, the arrangement of A.sup.1 and R.sup.5 O may be normal or reverse and may be regular or irregular,
- and wherein q is at least 2, when t is at least 2, and when u is at least 2, respectively, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
18 more elements
A method for producing a cement additive which comprises obtaining a crosslinked polymer by combining water-soluble polymers having a weight average molecular weight of 500 to 100,000 to one another by using a crosslinking agent which has a structural unit or is capable of forming at least one divalent group having the following formula (I):
- ##STR34## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR35## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR36## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5,
- said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein the water-soluble polymer comprises at least one member selected from the group consisting of ##STR37## wherein m is 0 or an integral number of 1 to 50;
- n is 0 or 1;
- M is at least one member of the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group, and an organic amine group,
- R.sup.5 and R.sup.6 independently denote an alkylene group of carbon number 2 to 4;
- R.sup.7 denotes an alkylene group of carbon number 1 to 5,
- with the proviso that when m is at least 2, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular, and
- wherein the water-soluble polymer further comprises at least one functional group selected from the group consisting of ##STR38## wherein p is an integral number of 1 to 10, q is 0 or an integral number of 1 to 100;
- r and s are, respectively, an integral number of 1 to 3;
- t and u are, respectively, an integral number of 1 to 100;
- A.sup.1 is a straight chain divalent or branched trivalent ring-opened group of an alkyleneimine of 2 to 4 carbon atoms;
- R.sup.8 denotes CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.9 denotes H, CH.sub.3, or C.sub.2 H.sub.5 ;
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5;
- and
- X.sup..crclbar. denotes an anionic pair ion,
- with the proviso that, when p is at least two, a plurality of A.sup.1 may be the same or different and, when a plurality of A.sup.1 are different from one another, their arrangement may be regular or irregular,
- with the proviso that when q is an integral number of from 1 to 100, the arrangement of A.sup.1 and R.sup.5 O may be normal or reverse and may be regular or irregular,
- with the proviso that when q is at least 2, when t is at least 2, and when u is at least 2, respectively, a plurality of R.sup.5 O may be the same or different and when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
19 more elements
A method for producing a cement additive which comprises obtaining a crosslinked polymer by combining water-soluble polymers having a weight average molecular weight of 500 to 100,000 to one another by using a crosslinking agent which has a structural unit or is capable of forming at least one divalent group having the following formula (I):
- ##STR39## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR40## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR41## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5,
- said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein the water-soluble polymer comprises --COOM and
- --COO--(R.sup.5 O).sub.u --R.sup.10
- wherein M is at least one member of the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group, and an organic amine group,
- R.sup.5 denotes an alkylene group of carbon number 2 to 4;
- u is an integral number of 1 to 100;
- and
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5,
- with the proviso that when u is at least 2, a plurality of R.sup.5 O may be the same or different and when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- wherein the water-soluble polymer is derived from a (poly)alkyleneglycol mono(meth)acrylate monomer (xiv) in an amount of 1 to 99.9% by weight and a (meth)acrylic monomer (i) in an amount of 99 to 0.1% by weight wherein the total (xiv) and (i) is 100% by weight and the crosslinking agent has a functional group capable of reacting with at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group being contained in the water-soluble polymer, and the crosslinking agent and the water-soluble polymer are used in a molar ratio range of 0.001 to 1.0 between a functional group of said crosslinking agent and a functional group of said water-soluble polymer wherein said monomer (i) has the structure:
- ##STR42## wherein M is at least one member selected from the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group and an organic amine group;
- and R.sup.3 denotes H or CH.sub.3 ;
- wherein said monomer (xiv) has the formula:
- ##STR43## wherein u is the integral number of 1 to 100;
- with the proviso that, when u is at least 2, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular;
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
15 more elements
A method for producing a cement additive which comprises obtaining a crosslinked polymer by a polymerization reaction of a monomer (e), which has at least two polymerizable double bonds and has as a structural unit at least one divalent group having the below-described formula (I) between the double bonds, with a monomer (f), which has one polymerizable double bond capable of copolymerizing with the double bond in (e) and is able to form a main chain structure capable of leading to a water-soluble polymer of a weight average molecular weight of 500 to 100,000 ##STR44## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR45## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR46## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5, said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein the water-soluble polymer comprises at least one group selected from the group consisting of ##STR47## wherein m is 0 or an integral number of 1 to 50;
- n is0 or 1;
- M is at least one member selected from the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group and an organic amine group;
- R.sup.5 and R.sup.6 independently denote an alkylene group of 2 to 4 carbon atoms;
- R.sup.7 denotes an alkylene group of 1 to 5 carbon atoms;
- with the proviso that when m is at least 2, a plurality of R.sup.5 O may be the same or different, and when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- and wherein the water-soluble polymer further comprises at least one group selected from the group consisting of ##STR48## wherein p is an integral number of 1 to 10;
- q is 0 or an integral number of 1 to 100;
- r and s are, respectively, an integral number of 1 to 3;
- t and u are, respectively, an integral number of 1 to 100;
- A.sup.1 is a straight chain divalent or branched trivalent ring-opened group of an alkyleneimine of 2 to 4 carbon atoms;
- R.sup.8 denotes CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.9 denotes H, CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5;
- and
- X.sup..crclbar. denotes an anionic pair ion,
- with the proviso that when p is at least two, a plurality of A.sup.1 may be the same or different and, when a plurality of A.sup.1 are different from one another, their arrangement may be regular or irregular;
- and with the proviso that when q is an integral number of from 1-100, the arrangement of A.sup.1 and R.sup.5 O may be normal or reverse and may be regular or irregular;
- and with the proviso that when q is at least 2, when t is at least 2, and when u is at least 2 respectively, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular;
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
18 more elements
A cement composition comprising cement, water and a cement additive comprising a crosslinked polymer in which, between main chains having a water-soluble polymer structure of a weight average molecular weight from 500 to 100,000, a bond having as a structural unit at least one divalent group having the following formula (I) is formed ##STR51## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR52## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR53## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5, said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein said main chains comprise at least one member selected from the group consisting of ##STR54## wherein m is 0 or an integral number of 1 to 50;
- n is 0 or 1;
- M is at least one member selected from the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group and an organic amine group;
- R.sup.5 and R.sup.6 independently denote an alkylene group of carbon number 2 to 4;
- R.sup.7 denotes an alkylene group of carbon number 1 to 5;
- with the proviso that when m is at least 2, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular;
- and wherein said main chains further comprise at least one functional group selected from the group consisting of ##STR55## wherein p is an integral number of 1 to 10;
- q is 0 or an integral number of 1 to 100;
- r and s are, respectively, an integral number of 1 to 3;
- t and u are, respectively, an integral number of 1 to 100;
- A.sup.1 is a straight chain divalent or branched trivalent ring-opened group of an alkyleneimine of 2 to 4 carbon atoms;
- R.sup.8 denotes CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.9 denotes H, CH.sub.3, or C.sub.2 H.sub.5 ;
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5;
- and
- X.crclbar. denotes an anionic pair ion,
- with the proviso that, when p is at least two, a plurality of A.sup.1 groups may be the same or different and, when a plurality of A.sup.1 are different from one another, their arrangement may be regular or irregular;
- and with the provision that when q is an integral number of from 1-100, the arrangement of A.sup.1 and R.sup.5 O may be normal or reverse and may be regular or irregular,
- and wherein q is at least 2, when t is at least 2, and when u is at least 2, respectively, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
18 more elements
A cement composition comprising cement, water and a cement additive obtained from a method for producing a cement additive which comprises obtaining a crosslinked polymer by combining water-soluble polymers having a weight average molecular weight of 500 to 100,000 to one another by using a crosslinking agent which has a structural unit or is capable of forming at least one divalent group having the following formula (I):
- ##STR56## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR57## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR58## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5,
- said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein the water-soluble polymer comprises at least one member selected from the group consisting of ##STR59## wherein m is 0 or an integral number of 1 to 50;
- n is 0 or 1;
- M is at least one member of the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group, and an organic amine group,
- R.sup.5 and R.sup.6 independently denote an alkylene group of carbon number 2 to 4;
- R.sup.7 denotes an alkylene group of carbon number 1 to 5,
- with the proviso that when m is at least 2, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular, and
- wherein the water-soluble polymer further comprises at least one functional group selected from the group consisting of ##STR60## wherein p is an integral number of 1 to 10, q is 0 or an integral number of 1 to 100;
- r and s are, respectively, an integral number of 1 to 3;
- t and u are, respectively, an integral number of 1 to 100;
- A.sup.1 is a straight chain divalent or branched trivalent ring-opened group of an alkyleneimine of 2 to 4 carbon atoms;
- R.sup.8 denotes CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.9 denotes H, CH.sub.3, or C.sub.2 H.sub.5 ;
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5;
- and
- X.sup..crclbar. denotes an anionic pair ion,
- with the proviso that, when p is at least two, a plurality of A.sup.1 may be the same or different and, when a plurality of A.sup.1 are different from one another, their arrangement may be regular or irregular,
- with the proviso that when q is an integral number of from 1 to 100, the arrangement of A.sup.1 and R.sup.5 O may be normal or reverse and max be regular or irregular,
- with the proviso that when q is at least 2, when t is at least 2, and when u is at least 2, respectively, a plurality of R.sup.5 O may be the same or different and when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
19 more elements
A cement composition comprising cement, water and a cement additive obtained from a method for producing a cement additive which comprises obtaining a crosslinked polymer by combining water-soluble polymers having a weight average molecular weight of 500 to 100,000 to one another by using a crosslinking agent which has a structural unit or is capable of forming at least one divalent group having the following formula (I):
- ##STR61## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR62## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR63## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5,
- said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein the water-soluble polymer comprises --COOM and ##STR64## wherein M is at least one member of the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group, and an organic amine group,
- R.sup.5 denotes an alkylene group of carbon number 2 to 4;
- u is an integral number of 1 to 100;
- and
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5,
- with the proviso that when u is at least 2, a plurality of R.sup.5 O may be the same or different and when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- wherein the water-soluble polymer is derived from a (poly)alkyleneglycol mono(meth)acrylate monomer (xiv) in an amount of 1 to 99.9% by weight and a (meth)acrylic monomer (i) in an amount of 99 to 0.1% by weight wherein the total (xiv) and (i) is 100% by weight and the crosslinking agent has a functional group capable of reacting with at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group being contained in the water-soluble polymer, and the crosslinking agent and the water-soluble polymer are used in a molar ratio range of 0.001 to 1.0 between a functional group of said crosslinking agent and a functional group of said water-soluble polymer wherein said monomer (i) has the structure:
- ##STR65## wherein M is at least one member selected from the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group and an organic amine group;
- and R.sup.3 denotes H or CH.sub.3 ;
- wherein said monomer (xiv) has the formula:
- ##STR66## wherein u is the integral number of 1 to 100;
- with the proviso that, when u is at least 2, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular;
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
13 more elements
A cement composition comprising cement, water and a cement additive obtained from a method for producing a cement additive which comprises obtaining a crosslinked polymer by a polymerization reaction of a monomer (e), which has at least two polymerizable double bonds and has as a structural unit at least one divalent group having the below-described formula (I) between the double bonds, with a monomer (f), which has one polymerizable double bond capable of copolymerizing with the double bond in (e) and is able to form a main chain structure capable of leading to a water-soluble polymer of a weight average molecular weight of 500 to 100,000 ##STR67## wherein R.sup.1 and R.sup.2 independently are selected from the group consisting of:
- ##STR68## with the proviso that R.sup.1 is not required if R.sup.2 is ##STR69## and wherein R and R' independently denote an alkyl group of carbon number of 1 to 5, said crosslinked polymer having a maximum viscosity of 100,000 cps in a 20% by weight aqueous solution or dispersion at a temperature of 20.degree. C.,
- wherein the water-soluble polymer comprises at least one group selected from the group consisting of ##STR70## wherein m is 0 or an integral number of 1 to 50;
- n is 0 or 1;
- M is at least one member selected from the group consisting of a hydrogen atom, a monovalent, divalent or trivalent metal group, an ammonium group and an organic amine group;
- R.sup.5 and R.sup.6 independently denote an alkylene group of 2 to 4 carbon atoms;
- R.sup.7 denotes an alkylene group of 1 to 5 carbon atoms;
- with the proviso that when m is at least 2, a plurality of R.sup.5 O may be the same or different, and when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular,
- and wherein the water-soluble polymer further comprises at least one group selected from the group consisting of ##STR71## wherein p is an integral number of 1 to 10;
- q is 0 or an integral number of 1 to 100;
- r and s are, respectively, an integral number of 1 to 3;
- t and u are, respectively, an integral number of 1 to 100;
- A.sup.1 is a straight chain divalent or branched trivalent ring-opened group of an alkyleneimine of 2 to 4 carbon atoms;
- R.sup.8 denotes CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.9 denotes H, CH.sub.3 or C.sub.2 H.sub.5 ;
- R.sup.10 denotes H or an alkyl group of carbon number 1 to 5;
- and
- X.sup..crclbar. denotes an anionic pair ion,
- with the proviso that when p is at least two, a plurality of A.sup.1 may be the same or different and, when a plurality of A.sup.1 are different from one another, their arrangement may be regular or irregular;
- and with the proviso that when q is an integral number of from 1-100, the arrangement of A.sup.1 and R.sup.5 O may be normal or reverse and may be regular or irregular;
- and with the proviso that when q is at least 2, when t is at least 2, and when u is at least 2 respectively, a plurality of R.sup.5 O may be the same or different and, when a plurality of R.sup.5 O are different from one another, their arrangement may be regular or irregular;
- and wherein said crosslinked polymer is capable of forming a water-soluble polymer by cleavage of the divalent group in an alkaline medium.
18 more elements
Dependencies are inferred from the claim text.