CN107207678A - It is used as the new copolymer of water reducer in hydraulic-composition - Google Patents
It is used as the new copolymer of water reducer in hydraulic-composition Download PDFInfo
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- CN107207678A CN107207678A CN201680008058.8A CN201680008058A CN107207678A CN 107207678 A CN107207678 A CN 107207678A CN 201680008058 A CN201680008058 A CN 201680008058A CN 107207678 A CN107207678 A CN 107207678A
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- 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
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- 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
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers 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
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- 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
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- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- 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
- C04B2103/302—Water reducers
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- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
Abstract
The present invention relates to the new copolymer by being polymerize by the monomer mixture comprising following components and being obtained：At least one anionic monomer (a) for including polymerizable unsaturated functional group and carboxyl；With the monomer (b) of at least one formula (I)：H2C=C (R1)‑(CH2)p‑O‑[(EO)n‑(PO)m] H (I), wherein [(EO)n‑(PO)m] represent as ethoxy unit EO and propoxy unit PO blocks, poly-alkoxyl chain formed by alternately or statistically distribution, molar ratio (n)/(m+n) of ethoxy unit is more than or equal to 70% and less stringent than 90% in poly-alkoxyl chain.The invention further relates to include the hydraulic-composition of this copolymer, such as concrete composition, and the copolymer is used as the purposes of water reducer in hydraulic-composition.
Description
Diminishing is used as the present invention relates to new copolymer and its in hydraulic-composition such as concrete and mortar material
The purposes of agent.
This based composition is intended to for all construction markets.
Hydraulic-composition, which is generally comprised, to be intended to improve the various chemical addition agents of its characteristic.In these additives, " subtract
Water " agent, also referred to as " dispersant ", " fluidizing reagent ", " plasticizer " or " superplasticizer ", with improvement composition chats composition granule
The function of dispersity.These chemical reagent cause the water content of hydraulic-composition to reduce, and this makes it possible to improve these groups
The performance quality of compound, especially their mechanical strength.
The various dispersants for hydraulic-composition have been proposed.The chemical composition of these reagents and containing
There is characteristic caused in their compositions different.
In history, the first compound proposed as dispersant is the lignin sulfonic acid as described in US3772045
Salt.Then using formaldehyde and the condensation polymer of naphthalene or melamine sulfonate/ester, as lifted in US3359225 and US4258790
Example explanation.
Recently, a kind of new dispersant family being made up of combed carboxylic acid polyalcohol has been developed.Usually, these gather
It is usually the main chain of (methyl) acrylic acid property and using hydrophilic radical such as side chain of the polyoxy pendent alkyl groups as end group that compound, which has,.
For example, WO97/39037 is described by using acrylic monomers and polyether macromonomer such as oxygen ethene
(methyl) acrylate and oxypropylene (methyl) acrylate are polymerize to synthesize comb-shaped polymer, and it may be used as in cement
Water reducer.
The dispersed copolymer proposed in WO2006/028252 can also be referred to.
CN1148329C also proposed the copolymer as the dispersant for cement, its by monocarboxylic acid type monomer such as
(methyl) acrylic acid and the monomer of polyalkylene glycol ethers type are polymerize and obtained, the monomer of polyalkylene glycol ethers type
The ratio of middle ethoxy unit is at least 90 moles % of whole oxyalkyl units, and the monomer of the polyalkylene glycol ethers type is excellent
Select polyglycol ether.
JP2006/282414 is related to the reagent for forming high strength cement.It contains (a) glycerine as key component
Or the copolymer of glycerol derivatives and (b) based on the polycarboxylic acids with poly (oxyalkylene) fundamental mode compound on side chain.
US6211317 describes olefinically unsaturated carboxylic acid derivatives, oxyalkylene glycol alkenyl ethers, unsaturated dicarboximide
Or the emulsion copolymers of acid amides and vinyl monomer.Them are described as the additive of hydraulic cementing materials particularly cement
Purposes.
KR10086040 describes the unsaturated monomer based on the polyalkylene ether for being supplemented with least two aklylene glycols
The copolymer of (methyl) acrylate monomer.Which depict their purposes as cement additire.
The present invention is directed to propose new dispersant, the water content of hydraulic-composition is preferably reduced to realize, without damaging
Its mobility of evil or workability.
More specifically, according to its one side, the present invention relates to by using the monomer mixture comprising following components
The copolymer for being polymerize and being obtained：
- at least one the anionic monomer (a) for including polymerizable unsaturated functional group and carboxyl；With
The monomer (b) of-at least one formula (I)：
H2C=C (- R1)-(CH2)p–O–[(EO)n–(PO)m]–H(I)
Wherein：
R1Represent hydrogen atom or CH3Group；
P is 1 or 2；
[(EO)n-(PO)m] represent by ethoxy unit EO and propoxy unit PO blocks, it is alternately or randomly distributed
And the poly-alkoxyl chain constituted,
M and n represent 1 to 250 integer, and m and n summation are more than or equal to 10, and condition is ethyoxyl in poly-alkoxyl chain
The molar ratio (n) of unit/(m+n) is more than or equal to 70% and less stringent than 90%.
Comprising the unit for being at least derived from anionic monomer (a) and the unit of monomer (b) derived from formula (I) such as the upper limit
Fixed copolymer is in this paper remainder referred to as " according to the copolymer of the present invention ".
Unexpectedly, the inventors have discovered that this copolymer make it possible to significantly decrease wherein apply this be total to
The amount of the hydraulic-composition reclaimed water of polymers.
Hence it is advantageous to, can conduct according to the copolymer of the present invention as illustrated in experiment test below
Additive in hydraulic-composition, as " diminishing " agent, or even is used as " efficient diminishing " agent application.
In the present case, term " diminishing " agent or " plasticizer " refer to according to standard ADMIXTURE NF EN
934-2 allows the concrete through admixture relative to the reagent of the water reduction of control concrete at least 5%." high efficiency water reducing agent " or
" superplasticizer " is to allow the concrete through admixture relative to the additive of the water reduction of control concrete at least 12%.
In addition, this water, which is reduced, will not produce the infringement of the performance quality to hydraulic-composition such as concrete, especially
Its mobility or workability.In other words, for identical workability, given hydraulicity combination is allowed according to the copolymer of the present invention
The water content reduction of thing such as concrete.
As being described in detail in embodiments below, the dispersing characteristic of water reducer can be according to standard EN in hydraulic-composition
12350-2 is evaluated by measuring the slump.Slump value is bigger, and hydraulic-composition workability is better.Specifically, keep
The good initial workability of hydraulic-composition such as concrete is vital, because the performance determines that it is applied, such as
For filling template.
According to other features, advantage and the application mode of the copolymer of the present invention after following description and embodiment is read
Will become more apparent that ground is displayed, it is provided as non-limitative illustration.
In this paper remainder, statement " ... and ... between ", " from ... extremely ... " and " from ... change
Extremely ... " it is equivalent and is intended to mean that including end points, unless otherwise indicated.
Unless otherwise stated, statement " contain/including " be interpreted as refer to " containing/comprising at least one ".
The copolymer of the present invention：
As it was previously stated, being polymerize according to the copolymer of the present invention by using at least following components and being obtained：
- one or more include the anionic monomer of polymerizable unsaturated functional group and carboxyl, in remaining of this paper
It is referred to as " monomer (a) " in part；With
The monomer of the lower formula (I) of-one or more, is referred to as " monomer (b) " in this paper remainder,
H2C=C (- R1)-(CH2)p–O–[(EO)n–(PO)m]–H(I)
Wherein：
R1Represent hydrogen atom or CH3Group；
P is 1 or 2；
[(EO)n-(PO)m] represent by ethoxy unit EO and propoxy unit PO blocks, it is alternately or randomly distributed
And the poly-alkoxyl chain constituted,
M and n represent 1 to 250 integer, and m and n summation are more than or equal to 10, and condition is ethyoxyl in poly-alkoxyl chain
The molar ratio (n) of unit/(m+n) is more than or equal to 70% and less stringent than 90%.
Other polymerizable monomers can optionally be included according to the copolymer of the present invention.Optionally it is comprised in the present invention
Optional monomers in the composition of copolymer can have different property, as this paper remainder is described in detail.
Especially, the monomer (b) of the anionic monomer (a) and the formula (I) can account for the compositing monomer of copolymer
More than 80 moles % of total moles, particularly greater than 90 moles %, more particularly greater than 95 moles of %.
According to the change programme of implementation, according to the copolymer of the present invention only by the unit shape derived from monomer (a) He (b)
Into.In other words, can be by using by one or more of anionic monomers (a) and one kind or many according to the copolymer of the present invention
The monomer mixture of monomer (b) formation of the formula of kind (I) is polymerize and obtained.
In the copolymer according to the present invention, the distribution of the unit derived from monomer (a) and the unit derived from monomer (b)
Can be block type, alternate type or random.According to an embodiment, it is random distribution or is alternately distributed.According to another
Individual embodiment, it is distributed for block type.
It can be polymerize according to the copolymer of the present invention by using monomer mixture composed of the following components and be obtained
：
- at least one the anionic monomer (a) for including polymerizable unsaturated functional group and carboxyl；With
The monomer (b) of-at least one formula (I)：
H2C=C (- R1)-(CH2)p–O–[(EO)n–(PO)m]–H(I)
Wherein：
R1Represent hydrogen atom or CH3Group；
P is 1 or 2；
[(EO)n-(PO)m] represent by ethoxy unit EO and propoxy unit PO blocks, it is alternately or randomly distributed
And the poly-alkoxyl chain constituted,
M and n represent 1 to 250 integer, and m and n summation are more than or equal to 10, and condition is ethyoxyl in poly-alkoxyl chain
The molar ratio (n) of unit/(m+n) is more than or equal to 70% and less stringent than 90%.
The monomer (a) and the amount of (b) applied are equivalent to 100 weights for forming the monomer total amount according to copolymer of the invention
Measure %.
Anionic monomer (a) with polymerizable unsaturated functional group and carboxyl：
The anionic monomer (a) included in the composition of the copolymer according to the present invention can be chosen more particularly from propylene
The mixture of acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid and these monomers.
The monomer (a) can be sour form, such as carboxylic acid and/or salt form, such as carboxylate.
It should be understood that the mixture of only a kind of monomer (a) or several different monomers (a) can be contained according to the present invention
Copolymer composition in.For example, it can be the mixture of acrylic monomers and methacrylic acid monomer, or Malaysia
The mixture of acid, acrylic acid and methacrylic acid monomer.
According to specific embodiment, formed according to the copolymer of the present invention by least acrylic acid and/or methacrylic acid,
Especially formed by least acrylic acid (AA).
According to the change programme of implementation, the anionic monomer included in the composition of the copolymer according to the present invention
(a) acrylic acid and methacrylic acid and its mixture are selected from.
According to specific embodiment, the anionic monomer (a) can account in the copolymer according to the present invention and constitute single
50 moles of % to 99 moles of % of the total moles of body, particularly 60 moles of % to 95 of % to 95 moles of %, especially 70 moles
Mole % to 90 moles of % of %, more particularly 80 moles.
The monomer (b) of formula (I)：
As it was previously stated, the monomer (b) included in the composition of the copolymer according to the present invention corresponds to following formula (I)：
H2C=C (- R1)-(CH2)p–O–[(EO)n–(PO)m]–H(I)
Wherein：
R1Represent hydrogen atom or CH3Group；
P is 1 or 2；
[(EO)n-(PO)m] represent the poly-alkoxyl chain that is made up of ethoxy unit EO and propoxy unit PO；
M and n represent 1 to 250 integer, and m and n summation are more than or equal to 10, and condition is ethyoxyl in poly-alkoxyl chain
The molar ratio (n) of unit/(m+n) is more than or equal to 70% and less stringent than 90%.
Term " poly-alkoxyl " chain refers to the chain of poly- (aklylene glycol) type.Term " poly- (aklylene glycol) " refers to derive
From the polymer of the aklylene glycol of olefinic oxide.
According to poly- (aklylene glycol) chain of the monomer (b) of the present invention by with formula-CH2-CH2- O-, represented with " EO "
Ethyoxyl (or " ethylidene oxygen ") unit and by with formula-CH2-CH(CH3)-O-, the propoxyl group that is represented with " PO " it is (or " sub-
Propyl group oxygen ") unit formed.
Schema states " [(EO)n-(PO)m] " without the order for assuming ethyoxyl and propoxy unit in poly-alkoxyl chain.Tool
Body, poly-alkoxyl chain can have the distribution of the EO and PO units of block type, random or alternate type.
According to specific embodiment, it is distributed EO and PO unit blocks.
Especially, the poly-alkoxyl chain of monomer (b) can be diblock type, and can by polyoxyethylene block and
Polyoxypropylene block is formed.
According to the change programme of implementation, the p in above-mentioned formula (I) is 1.
In other words, according to the change programme of the present embodiment, the institute included in the composition of the copolymer according to the present invention
Monomer (b) is stated corresponding to following formula (I ')：
H2C=C (- R1)–CH2–O–[(EO)n–(PO)m]–H(I’)
Wherein R1, n and m be as previously defined.
According to specific embodiment, according to the copolymer of the present invention by least one above-mentioned formula (I) or the monomer of (I ')
(b) formed, wherein R1Represent methyl.
Especially, according to specific embodiment, according to the present invention copolymer by least one lower formula (II) monomer
(b) formed：
H2C=C (- CH3)–CH2–O–[(EO)n–(PO)m]–H(II)
Wherein n and m are as previously defined.
As it was previously stated, schema statement " [(EO)n-(PO)m] " without ethoxy unit and propoxyl group in hypothesis poly-alkoxyl chain
The order of unit.Poly-alkoxyl chain can have EO the and PO units of block type, random or alternate type, particularly block type
Distribution.
According to a specific embodiment, according to the copolymer of the present invention by least one lower formula (III) monomer (b)
Obtain：
M and n are as previously defined.
In above-mentioned formula (III), poly-alkoxyl chain is by the first polyoxyethylene block and the second polyoxypropylene block shape
Into.
According to the change programme of another implementation, the p in above-mentioned formula (I) is 2.
In other words, according to the change programme of the implementation, the list included in the composition of the copolymer according to the present invention
Body (b) corresponds to following formula (I ")：
H2C=C (- R1)–CH2–CH2–O–[(EO)n–(PO)m]–H(I”)
Wherein R1, n and m be as previously defined.
According to specific embodiment, according to the copolymer of the present invention by least one above-mentioned formula (I ") monomer (b) shape
Into wherein R1Represent methyl.
According to specific embodiment, formed according to the copolymer of the present invention by the monomer (b) of at least one lower formula (IV)：
H2C=C (- CH3)–CH2–CH2–O–[(EO)n–(PO)m]–H(IV)
Wherein n and m are as previously defined.
As it was previously stated, schema statement " [(EO)n-(PO)m] " without ethyoxyl and propoxy unit in hypothesis poly-alkoxyl chain
Order.Poly-alkoxyl chain can have point of block type, random or alternate type, the particularly EO and PO units of block type
Cloth.
According to specific embodiment, obtained according to the copolymer of the present invention by the monomer (b) of at least one lower formula (V)：
H2C=C (- CH3)–CH2–CH2–O–(EO)n–(PO)m–H(V)
M and n are as previously defined.
In above-mentioned formula (V), poly-alkoxyl chain is formed by the first polyoxyethylene block and the second polyoxypropylene block.
As for anionic monomer (a), it should be understood that there was only the mixture of a kind of monomer (b) or several different monomers (b)
It can be contained in the composition according to the copolymer of the present invention.
Therefore, according to specific embodiment, according to the copolymer of the present invention by least one wherein R1Represent hydrogen atom
Formula (I) monomer (b1) and at least one wherein R1Represent the monomer (b of the formula (I) of methyl2) at least one mixture obtain
.
Especially, can be by least one wherein R according to the copolymer of the present invention1Represent the above-mentioned formula (I ') of hydrogen atom
Monomer (b1') and at least one wherein R1Represent the monomer (b of the above-mentioned formula (I ') of methyl2') (that is, the monomer of above-mentioned formula (II)
(b2')) at least one mixture obtain.
In the case of the specific embodiment, the monomer included in the composition of the copolymer according to the present invention
(b1') and the monomer (b2') can be with 10 to 0.01, particularly 1 to 0.1 monomer (b1')/monomer (b2') mol ratio is in fact
Apply.
, can be by least one above-mentioned formula (I ') according to the copolymer of the present invention according to another specific embodiment
Monomer (b1') and at least one above-mentioned formula (I ") monomer (b2") at least one mixture obtain.Especially, according to the present invention
Copolymer can be by least one wherein R1Represent the monomer (b of the above-mentioned formula (I ') of methyl1') (that is, the list of above-mentioned formula (II)
Body (b1')) and at least one wherein R1Represent the monomer (b of the above-mentioned formula (I ") of methyl2") (that is, the monomer of above-mentioned formula (IV)
(b2")) at least one mixture obtain.
According to the essential characteristic of the monomer (b) included in the composition of the copolymer of the present invention, second in poly-alkoxyl chain
Epoxide unit EO molar ratio ((n)/(m+n) in i.e. above-mentioned formula (I), (I '), (II) or (III)) is more than or equal to 70%
And strictly less than 90%.
Especially, ethoxy unit EO molar ratio can be 70% to 88%, be particularly greater than in poly-alkoxyl chain
Or equal to 72%, more specifically greater than or equal to 75%.
According to specific embodiment, ethoxy unit EO molar ratio can be less than or equal in poly-alkoxyl chain
85%th, it is particularly smaller or equal than 80%.
Mol ratio in poly-alkoxyl chain between ethoxy unit and propoxy unit can be more specifically 2.5 to 8, spy
It is not 2.8 to 7.5, especially 3 to 6.
As it was previously stated, in the poly-alkoxyl chain of monomer (b) ethoxy unit and propoxy unit sum (that is, m and n's
With) it is more than or equal to 10.
According to specific embodiment, it can be 10 to 150, particularly 18 to 110, more particularly 20 to 70.
Therefore, according to the present invention monomer (b) poly-alkoxyl chain can have 450 grams/mol to 7500 grams/mol,
Particularly 900 grams/mol to 5500 grams/mol, more particularly 1000 grams/mol to 3500 grams/mol of mumber average molar mass.
It should be understood that different change programmes given above and specific embodiment can combine other to limit as much as possible
Change programme or specific embodiment.
Can be by technology well known by persons skilled in the art, by using in allyl alcohol according to the monomer (b) of the present invention
Or the polymerization of ethylidene oxygen monomer and propyleneoxy monomers is prepared to increase desired poly-alkoxyl chain on methallyl alcohol.
According to specific embodiment, the monomer (b) can account for compositing monomer in the copolymer according to the present invention and rub
1 mole of % to 50 moles of % of your sum, particularly % to 30 moles of % of 5 moles of % to 40 moles of %, especially 5 moles, more
10 moles of % to 20 moles of % in particular.
The monomer (b) can in a variety of manners, especially solid form, particularly powder or sheet form or liquid shape
Formula (liquid or the aqueous solution of monomer (b) that are formed by monomer (b)) is applied.
Especially, monomer (b) is water miscible.
Preferably, the monomer (b) in liquid form, is particularly implemented with the aqueous solution, and the form is specifically adapted for root
According to the synthesis of the copolymer of the present invention.
Between the anionic monomer (a) and the monomer (b) that are included in the composition of the copolymer according to the present invention
Mol ratio can with more particularly 1 to 99, particularly 2.3 to 19, more particularly 4 to 9.
Optional monomer：
As it was previously stated, according to the copolymer of the present invention can by using except the monomer (a) and the monomer (b) it
The monomer mixture also comprising one or more of other monomers is polymerize and obtained outside, and the other monomer is different from
Monomer (a) and (b), this paper remainder its represented with " monomer (c) ".
Other monomer (c) can be chosen more particularly from：
- 2- acrylamido -2- methyl propane sulfonic acids (AMPS)；
- vinylsulfonate, particularly SSS；
- amine；
- the ester containing hydroxyl, such as hydroxyethyl methacrylate (HEMA), hydroxy-ethyl acrylate, methacrylic acid hydroxypropyl
Ester and hydroxypropyl acrylate；
- polyalkene glycol acrylate phosphate or aklylene glycol methacrylate phosphate, particularly ethylene glycol
Methacrylate phosphate or ethylene glycol acrylate phosphate；
- acrylamide or Methacrylamide；
- phosphonic acid monomer, such as alkyl vinyl phosphonate ester and phosphonate ester；
The macromonomer of-lower formula (VI)：
Ra–[(EO)q–(PO)r–(BO)s]–Ra’(VI)
Wherein：
[(EO)q-(PO)r-(BO)s] represent by selected from ethoxy unit EO, propoxy unit PO and butoxyl unit BO
Oxyalkyl units block, alternately or it is randomly distributed and constitute poly-alkoxyl chain；
Q, r and s represent 0 or 1 to 250 integer independently of one another, and m, n and p summation are 10 to 250；
RaRepresent the group of the mixture selected from acrylate, methacrylate and these esters；With
Ra' represent hydrogen or the alkyl containing 1 to 4 carbon atom；
The hydrophobic monomer of-lower formula (VII)：
Rb–[(EO)t–(PO)u–(BO)v]–Rb’(VII)
Wherein：
[(EO)t-(PO)u-(BO)v] represent by selected from ethoxy unit EO, propoxy unit PO and butoxyl unit BO
Oxyalkyl units block, alternately or it is randomly distributed and constitute poly-alkoxyl chain；
T, u and v represent 0 or 1 to 250 integer independently of one another, and m, n and p summation are 10 to 250；
RbRepresent the group of the mixture selected from acrylate, methacrylate and these esters；With
Rb' alkyl containing 8 to 40 carbon atoms is represented,
Cross-linking monomer.
According to specific embodiment, in above-mentioned formula (VI), s is equal to 0；Q and r represent 1 to 250, such as 10 to 150 or
10 to 100 integer.
According to specific embodiment, in above-mentioned formula (VII), v is equal to 0；T and u represent 1 to 250, such as 10 to 150
Or 10 to 100 integer.
The other monomer (c) is also selected from cross-linking monomer.
Can be for example comprising single cross-linking monomer according to the copolymer of the present invention.
According to another embodiment, it includes two kinds of different cross-linking monomers.
Cross-linking monomer can have hydrophilic nmature, hydrophobic property or amphipathic characteristic.
The example of these compounds includes two (methyl) acrylate compounds, such as PAG two (methyl) propylene
Acid esters, especially polypropylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) third
Olefin(e) acid ester, triethylene glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,6- butanediols two (methyl)
Acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, (first of 1,9- nonanediols two
Base) acrylate and 2,2 '-bis- (4- (acryloyl-oxy propoxyphenyl) propane, 2,2 '-bis- (4- (acryloyl-oxy diethoxies
Base phenyl) propane and zinc acrylate resin；Three (methyl) acrylate compounds, such as trimethylolpropane tris (methyl) acrylate,
Trimethylolethane trimethacrylate (methyl) acrylate, (methyl) acrylate of pentaerythrite three and tetramethylol methane three (methyl) third
Olefin(e) acid ester；Four (methyl) acrylate compounds, such as two (trihydroxy methyl) propane four (methyl) acrylate, tetramethylol methane
Four (methyl) acrylate and pentaerythrite four (methyl) acrylate；Six (methyl) acrylate compounds, such as two seasons penta 4
Alcohol six (methyl) acrylate；Five (methyl) acrylate compounds, such as dipentaerythritol five (methyl) acrylate；Pi-allyl
Compound, such as pi-allyl (methyl) acrylate, diallyl phthalate, diallyl itaconate, the allyl of fumaric acid two
Ester and diallyl maleate；Per molecule contains many allylsucrose ethers of 2 to 8 groups, many Allyl pentaerythritol ethers, such as
Pentaerythritol diallyl ether, pentaerythritol triallyl ether and pentae-rythritol tetraallyl ether；Many pi-allyl trihydroxy methyls third
Alkane ether, such as diallyl trimethylolpropane ether and triallyl trimethylolpropane ether.Other polyunsaturated compounds include
Divinyl glycol, divinylbenzene, divinyl cyclohexyl and methylene-bisacrylamide.
According on the other hand, cross-linking monomer can pass through polyalcohol and unsaturated acid anhydride such as maleic anhydride, itaconic anhydride
(methyl) acrylic anhydride esterification or by with isocyanates such as 3- isopropenyls dimethyl benzene isocyanates plus
Prepared into reaction.
Following compound can also be used to obtain cross-linking monomer：Polyhalo alkanol, such as 1,3- dichloroisopropanols and 1,3-
Dibromo isopropanol；Halogenated epoxy alkane such as epoxychloropropane, epoxy bromopropane, 2- methyl epichlorohydrins and Epiiodohydrin；
Polyglycidyl ether, such as BDDE, glycerine 1,3- diglycidyl ethers, ethylene glycol diglycidyl
Ether, propylene glycol diglycidylether, diethylene glycol diglycidyl glycerin ether, neopentylglycol diglycidyl ether, polypropylene glycol two contract
Water glycerin ether, bisphenolA-epichlorohydrin epoxy resin and its mixture.
According to specific embodiment, cross-linking monomer is selected from at least two polymerizable ethylenical unsaturated double bonds
(methyl) acrylate (such as by (methyl) acrylic acid and the straight chain containing 2 to 12 carbon atoms and at least two hydroxyls or
It is prepared by the esterification of branched polyalcohol), polyalkenyl polyether containing at least two polymerizable ethylenical unsaturated double bonds
(for example pass through alkenyl halide and the straight chain containing 2 to 12 carbon atoms and at least two hydroxyls or branched polyalcohol
Etherificate prepare) and these cross-linking monomers mixture.
According to one embodiment of the invention, copolymer includes two kinds of cross-linking monomers：
- first cross-linking monomer is (methyl) acrylate containing at least two polymerizable ethylenical unsaturated double bonds
(for example pass through (methyl) acrylic acid and the straight chain containing 2 to 12 carbon atoms and at least two hydroxyls or branched polyalcohol
Esterification prepare), and
- second cross-linking monomer is the polyalkenyl polyether containing at least two polymerizable ethylenical unsaturated double bonds
(for example pass through alkenyl halide and the straight chain containing 2 to 12 carbon atoms and at least two hydroxyls or branched polyalcohol
Etherificate prepare).
According to another embodiment, copolymer, which is included, has two kinds of cross-linking monomers of different nature, such as trihydroxy methyl
Propane three (methyl) acrylate (TMPTA or TMPTMA) and trimethylolpropane allyl ether (TMPDAE).
It should be understood that to the other monomer applied, such as the content of cross-linking monomer is adjusted in order to avoid changing copolymer
Desired characteristic.
Generally, the other monomer (c) can account for the total moles of compositing monomer in the copolymer according to the present invention
Less than 20 moles %, especially less than 15 moles %, especially less than 10 moles %, more particularly less than 5 moles of %.
For the various embodiments described by every kind of monomer for including in the composition of the copolymer according to the present invention
It can combine.
According to specific embodiment, according to the copolymer of the present invention therefore can by using comprising or even by following
The monomer mixture of component formation is polymerize to obtain：
Anionic monomer of-the one or more selected from acrylic acid, methacrylic acid and its mixture, particularly acrylic acid
(a)；With
- there is above-mentioned formula (I '), one or more of monomers (b) of above-mentioned formula (II), wherein ethoxy unit are particularly
It is distributed with propoxy unit more particularly block.
According to specific embodiment, according to unit of the copolymer of the present invention comprising at least derived from propylene acid and as before
The described unit derived from formula (II), the particularly monomer of formula (III).
According to the first specific embodiment, obtained according to the copolymer of the present invention by the polymerization of at least following components：
- 50 moles of % to 99 moles of % at least one anionic monomer (a), particularly as previously defined；With
The monomer (b) of -1 mole of % to 50 moles of % at least one formula (I), particularly as previously defined,
The mole percent of every kind of monomer is that the total moles of the compositing monomer relative to copolymer are represented.
According to the second specific embodiment, obtained according to the copolymer of the present invention by the polymerization of at least following components：
- 70 moles of % to 95 moles of % at least one anionic monomer (a), particularly as previously defined；With
The monomer (b) of -5 moles of % to 30 moles of % at least one formula (I), particularly as previously defined,
The mole percent of every kind of monomer is that the total moles of the compositing monomer relative to copolymer are represented.
According to the 3rd specific embodiment, obtained according to the copolymer of the present invention by the polymerization of at least following components：
- 80 moles of % to 90 moles of % at least one anionic monomer (a), particularly as previously defined；With
The monomer (b) of -10 moles of % to 20 moles of % at least one formula (I), particularly as previously defined,
The mole percent of every kind of monomer is that the total moles of the compositing monomer relative to copolymer are represented.
According to these three specific embodiments, the summation of the mole percent of monomer (a) and monomer (b) is equal to 100%.Change
Yan Zhi, according to these three embodiments of the present invention, copolymer is with specified only by the unit derived from monomer (a) and (b)
Mol ratio formation.
According to the present invention copolymer can have 15000 grams/mol to 250000 grams/mol, particularly 20000 grams/
Mole to 200000 grams/mol, more particularly 25000 grams/mol to 175000 grams/mol of weight average molecular weight Mw.
Weight average molecular weight or Mw can be determined by SEC (SEC), such as more specific in embodiments below
Description.
Can be with stoichiometry or the shape of non-stoichiometric, mixing or non-mixed salt according to the copolymer of the present invention
Prepared by formula, it is possible to prepared with alkali metal, alkaline-earth metal, amine or quaternary ammonium.
It is the form of acid according to the copolymer of the present invention according to specific embodiment.
It is the form being neutralized according to the copolymer of the present invention according to another embodiment.
It is the form being partially or completely neutralized according to the copolymer of the present invention according to further embodiment.
According to specific embodiment, copolymer, which is used, is selected from potassium ion, sodium ion, lithium ion, calcium ion, magnesium ion, ammonium
The ion of the mixture of ion, diethanol ammonium ion and these ions is neutralized.
According to the copolymer of the present invention can by conventional polymerization technique using monomer (a), (b) and (c) optionally come
Prepare.
, can be by radical polymerization, especially by can according to the copolymer of the present invention according to the change programme of implementation
Radical polymerization is controlled to obtain.
Application field：
As it was previously stated, as the water reducer in hydraulic-composition being particularly effective according to the copolymer of the present invention.
According to its other side, the present invention is so as to being related to if the copolymer limited before in hydraulic-composition as subtracting
The purposes of aqua.
The invention further relates to the water reducer for hydraulic-composition, it is comprising one or more of common as previously defined
Polymers, or be even made up of one or more of copolymers as previously defined.
Preferably, water reducer is made up of the copolymer or the mixture of copolymer according to the present invention.
Water reducer can be applied in a variety of manners, particularly liquid form.It can be one according to the present invention in particular
Kind or more plant copolymer aqueous solution form, its solids content can with more particularly 25% to 65%, such as 30% to
60%.
According to its another aspect, the present invention relates to the combination of the hydraulicity comprising at least one copolymer according to the present invention
Thing.
Hydraulic-composition can have different properties.They can be intended to be used for manufacture slurries, putty, binder, mixed
Solidifying soil or mortar.They can include impurity, such as clay.These compositions can include latex, fiber, You Jiju in particular
Collective, inorganic aggregate, filler and/or CaCO3。
It can be used the hydraulic-composition of water reducer according to the present invention, such as concrete and mortar material can be with
Comprising various types of cement as hydraulicity adhesive, for example, cement CEM I as described in standard EN 197-1,
CEM II, CEM III, CEM IV and CEM V.Wherein, cement CEM I do not include any additive.However, it is possible to these water
Mud addition slag, flying dust or calcium filler or siliceous filler.Concrete composition can be the concrete of different intensity grades, for example
C20/25 to C100/115.
Hydraulic-composition can be more particularly in addition to copolymer according to the present invention also comprising water and extremely
A kind of few aqueous compositions of hydraulicity adhesive.It can also be optionally comprising one or more of other additives.
Hydraulicity adhesive can include at least one cement, such as Portland cement.The example that can also be referred to includes
The hydraulicity adhesive of alumina cement type and calcium sulphoaluminate cement.
Hydraulic-composition can be such as ready-mixed concrete.
Such as 8 weights of the gross weight relative to hydraulic-composition can be included according to the hydraulic-composition of the present invention
Measure % to 75 weight %, such as 10 weight % to 50 weight % or 10 weight % to 40 weight % hydraulicity adhesive.
For example it can be introduced according to the water reducer of the present invention when concrete is mixed.
Can be with the 0.05 weight % relative to composition total weight to 3 weight % copolymerization according to the water reducer of the present invention
Thing, particularly 0.25 weight % are applied to 2.5 weight % ratio.
For target hydraulic-composition, the amount of the adjustable water reducer according to the present invention of those skilled in the art.Diminishing
The consumption of agent depends primarily on the amount of hydraulicity adhesive in hydraulic-composition.
According to specific embodiment, included according to the hydraulic-composition of the present invention relative to the gross weight of composition：
- 2 weight % to 15 weight % water；
- 10 weight % to the 30 weight % hydraulicity adhesive comprising cement；With
- 0.05 weight % to 3 weight % one or more of copolymers according to the present invention.
According to the embodiment, 10 weight % to 60 weights can also be additionally comprised according to the hydraulic-composition of the present invention
Measure % sand.
According to specific embodiment, it can be wrapped relative to the gross weight of composition according to the hydraulic-composition of the present invention
Contain：
- 2 weight % to 15 weight % water；
- 10 weight % to the 30 weight % hydraulicity adhesive comprising cement；
- 0.05 weight % to 3 weight % one or more of copolymers according to the present invention.
- 10 weight % to 60 weight % sand；With
- 10 weight % to 60 weight % one or more of gravels.
It needn't elaborate any further, the present invention is not in any way limited to these specific embodiments.
According to the present invention hydraulic-composition may be embodied in routinely applied in hydraulic-composition field it is various into
Point, it increases in particular selected from sand, gravel, aggregation, flour filler or ultra-fine filling material, such as calcium carbonate or silica, defoamer
Thick dose, stabilizer, biocide or antiseptic, accelerator or retarder.
The invention further relates to be used to prepare the hydraulic-composition for particularly comprising water and oneself according to the water reducer of the present invention
The purposes of hydraulicity adhesive of the body comprising cement.
The present invention will be described by Examples below now, it is provided as the non-limitative illustration of the present invention.
Embodiment：
1. the preparation of hydraulic-composition：
1.1.The preparation of copolymer：
The measurement of molecular weight of copolymer：
The molecular mass of copolymer is determined by size exclusion chromatography (SEC).
This technology applies the WATERS equipped with two detectorsTMBoard liquid chromatograph.One in these detectors
By the static dynamic light scattering at 90 ° of angles with using VISCOTEKTM MALVERNTMThe viscosity measurement that viscosimeter detector is measured
Method is combined.Another in these detectors is WATERSTMBoard reflects concentration detector.
The size exclusion chromatography post that the liquid chromatograph is suitably selected equipped with those skilled in the art, is studied with separating
Various molecular weight polymer.Liquid elution is mutually containing 1%KNO3Aqueous phase.
In detail, in the first step, 0.9 dry weight % polymeric solution is diluted in SEC eluents, SEC eluents
For 1%KNO3Solution.Then resulting solution is filtered by 0.2 μm of filter.Then 100 μ L are injected into chromatograph and (washed
De- liquid：1%KNO3Solution).
Liquid chromatograph includes isocratic pump (WATERSTM515), its flow velocity is set to 0.8 ml/min.Chromatograph is also wrapped
Column oven is included, itself includes the following column system of series connection：6cm length, internal diameter are 40mm WATERSTM ULTRAHYDROGEL
GUARD COLUMN pre-columns, 30cm length, internal diameter are 7.8mm WATERSTMULTRAHYDROGEL linear columns and two 30cm length,
Internal diameter is 7.8mm WATERSTM120 ANGSTROM ULTRAHYDROGEL posts.
Detecting system is in itself by WATERS firstTMThe refraction detectors of RI 410 and the MALVERN of nextTM 270DUAL
DETECTOR viscosimeters and 90 ° of angle light scattering dual detector compositions.Column oven is reached 55 DEG C of temperature, refractometer is reached 45
DEG C temperature.
Chromatograph MALVERNTMPolyCALTMThe single 19k PEO standards calibrations of type.
·Copolymer A(not according to the present invention)：
Copolymer A is polymerize and obtained by using the monomer mixture formed by following components：
- 85.9 moles of % acrylic acid；With
- 4.1 moles of % methacrylic polyethylene glycol (Mw=2400 grams/mol).
Synthetic copolymer A scheme：
The chemical products used is：
- 0.33g ferrous sulfate (FeSO4·7H2O),
- 6.0g DMDO (1,8- dimercapto -3,6- dioxaoctane, No. CAS：14970-87-7),
- 891.8g 60% methacrylic polyethylene glycol (Mw=2400 grams/mol),
- 97.5g acrylic acid,
- 16.8g 35% aqueous hydrogen peroxide solution,
- 16.9g 40% sodium hydrogensulfite.
Ferrous sulfate, 20% DMDO and 90% 60% methylallyl polyethylene glycol are introduced and contain the anti-of 150g water
Answer in device.Reactor is heated to 55 DEG C to 60 DEG C.It is surplus by acrylic acid, containing DMDO and 60% methylallyl polyethylene glycol
Solution, aqueous hydrogen peroxide solution and the solution of sodium bisulfite of excess were abreast injected in reactor in 40 minutes 1 hour.Note
Penetrate effective 120g water to rinse, and reactor is kept for 30 minutes 1 hour at a temperature of 58 DEG C to 62 DEG C.
Product is cooled down, the 50%NaOH for then adding 109.4g is neutralized.
The copolymer A of acquisition has according to foregoing 160300 grams/mol measured of molecular weight.
·Copolymer B(according to the present invention)：
Copolymer B is polymerize and obtained by using the monomer mixture formed by following components：
- 83.4 moles of % acrylic acid；With
The monomer (b) of -16.6 moles of % formula (I '), wherein R1Represent CH3, poly-alkoxyl chain is with 1990 grams/mol
Average molar mass, it is formed by 75 moles of % ethoxy unit and 25 moles of % propoxy unit, ethoxy unit and
It is distributed propoxy unit block.
Synthetic copolymer B scheme：
The chemical products used is：
- 0.31g ferrous sulfate (FeSO4·7H2O),
- 2.0g DMDO,
- 297.3g monomer (b),
- 32.5g acrylic acid,
- 8.4g 35% aqueous hydrogen peroxide solution,
- 8.5g 40% sodium hydrogensulfite.
Ferrous sulfate, 20% DMDO and 90% 60% methylallyl polyether polyols are introduced and contain 50g
In the reactor of water.Reactor is heated to 55 DEG C to 60 DEG C.By acrylic acid, contain DMDO and 60% methylallyl polyoxy Asia
Solution, aqueous hydrogen peroxide solution and the solution of sodium bisulfite of the residue of alkyl diol were abreast noted in 40 minutes 1 hour
Enter in reactor.Injection-tube is rinsed with 120g water, and reactor is kept for 30 minutes 1 hour at a temperature of 58 DEG C to 62 DEG C.
Product is cooled down, the 50%NaOH for then adding 109.4g is neutralized.
The copolymer B of acquisition has according to foregoing 172500 grams/mol measured of molecular weight.
·Copolymer C(according to the present invention)：
Copolymer C is polymerize and obtained by using the mixture formed by following components：
- 87.2 moles of % acrylic acid；With
The monomer (b) of -12.7 moles of % formula (I '), wherein R1Represent CH3, poly-alkoxyl chain is with 2700 grams/mol
Average molar mass, it is formed by 88 moles of % ethoxy unit and 12 moles of % propoxy unit, ethoxy unit and
It is distributed propoxy unit block.
Synthetic copolymer C scheme：
Copolymer C is prepared according to the similar step described by being directed to copolymer B before.
The copolymer C of acquisition has according to foregoing 156900 grams/mol measured of molecular weight.
1.2. the preparation of hydraulic-composition：
In each test, hybrid standard sand (0/4) under agitation, cement (CEM I are passed through according to standard EN 480-1
52.5N Holcim), 4/11 and 11/22 gravel, water and defoamer prepare concrete (350kg/m3)。
Additive is not added to composition 1 (control).
Concrete preparation 2 to 4 fills the solution just like preceding prepared copolymer A, B and C respectively.
In order to prepare the concrete preparation 2 to 4 for being respectively incorporated into copolymer A, B and C, adjust water/cement weight ratio to keep
The initial workability similar with compareing concrete.
Thus the ratio of every kind of component of the hydraulic-composition prepared is as shown in Table 1 below.
2.The evaluation of hydraulic-composition：
It is special according to initial fluidity (workability in T0), air capture and the diminishing that following scheme evaluates composition
Property.
Workability measurement in T0：
According to standard EN 12350-2, using being referred to as the conical butt being made up of galvanized steel of Abrams cones without base cone
The measurement of initial fluidity (or workability in T0) is carried out at room temperature.The cone has following characteristics：Upper diameter：100
± 2mm, lower diameter：200 ± 2mm, height：300±2mm.
Cone is placed on the plate soaked with sponge.
Then with every kind of preparation filling cone of specified rate.Filling continues 2 minutes.With metal bar by the content pressure of cone
Tightly.
In end-of-fill, cone is vertically risen, this causes its content to collapse onto plate.
According to standard EN 206-1, concrete can be classified according to its workability.
The measurement of water reduction：
This is measured according to standard ADMIXTURE NF EN 934-2.
It is given in Table 1 below for the result that various hydraulic-compositions are obtained.
Table 1
Hydraulic-composition all has uniform outward appearance, without the separation of component.
The amount of hydraulic-composition reclaimed water is enabled to reduce 36% respectively according to the copolymer B and C of the present invention application
With 28%, while keeping the initial fluidity (workability) similar to the initial fluidity initial fluidity of negative control.
It can be characterized as meeting standard ADMIXTURE NF EN 934-2 " efficient diminishing according to the copolymer of the present invention
Agent ", according to the standard, term " high efficiency water reducing agent " or " superplasticizer " are defined as allowing the concrete through admixture relative to control
The water of concrete at least 12% is reduced.
Therefore, it was demonstrated that when with application not according to the copolymer A of the present invention compared with when (15%), according to the copolymerization of the present invention
Thing (copolymer B and C) makes it possible to significantly decrease the amount (reducing 36% and 28% respectively) of hydraulic-composition reclaimed water, without
Influence the workability of the hydraulic-composition.
Claims (15)
1. a kind of copolymer for being polymerize and being obtained by using the monomer mixture comprising following components：
- at least one the anionic monomer (a) for including polymerizable unsaturated functional group and carboxyl；With
The monomer (b) of-at least one formula (I)：
H2C=C (- R1)-(CH2)p–O–[(EO)n–(PO)m]–H(I)
Wherein：
R1Represent hydrogen atom or CH3Group；
P is 1 or 2；
[(EO)n-(PO)m] represent by ethoxy unit EO and propoxy unit PO blocks, alternately or randomly distributed and structure
Into poly-alkoxyl chain；
M and n represent 1 to 250 integer, and m and n summation are more than or equal to 10, and condition is second described in the poly-alkoxyl chain
The molar ratio (n) of epoxide unit/(m+n) is more than or equal to 70% and less stringent than 90%.
2. the copolymer according to preceding claims, wherein the monomer (b) has with following formula (I ')：
H2C=C (- R1)–CH2–O–[(EO)n–(PO)m]–H (I’)
Wherein, R1, n and m be as defined in claim 1.
3. copolymer according to claim 1 or 2, it is characterised in that the copolymer is by least one lower formula (II)
Monomer (b) formation：
H2C=C (- CH3)–CH2–O–[(EO)n–(PO)m]–H (II)
Wherein, n and m are as defined in claim 1.
4. copolymer according to any one of the preceding claims, it is characterised in that the copolymer is under at least one
Monomer (b) formation of formula (III)：
M and n are as defined in claim 1.
5. copolymer according to any one of the preceding claims, wherein described in the poly-alkoxyl chain of the monomer (b)
The molar ratio of ethoxy unit is 70% to 88%, is particularly greater than or equal to 75%, especially less than or equal to 85%, spy
It is not less than or equal to 80%.
6. copolymer according to any one of the preceding claims, wherein ethoxy in the poly-alkoxyl chain of the monomer (b)
The sum (m+n) of base unit and propoxy unit is 10 to 150, particularly 18 to 110, more particularly 20 to 70.
7. copolymer according to any one of the preceding claims, wherein the monomer (b) accounts for the component of the copolymer
1 mole of % to 50 moles of % of total moles, particularly % to 30 moles of % of 5 moles of % to 40 moles of %, especially 5 moles,
More particularly 10 moles % to 20 moles of %.
8. copolymer according to any one of the preceding claims, wherein the anionic monomer (a) is selected from acrylic acid, first
Base acrylic acid, maleic acid, itaconic acid, the mixture of crotonic acid and these monomers, in particular selected from acrylic acid, methacrylic acid
And its mixture.
9. copolymer according to any one of the preceding claims, wherein the monomer (a) accounts for the composition of the copolymer
50 moles of % to 99 moles of % of the total moles of monomer, particularly 60 moles of % of % to 95 moles of %, especially 70 moles are extremely
% to 90 moles of % of 95 moles of %, more particularly 80 moles.
10. copolymer according to any one of the preceding claims, it is by using except the anionic monomer (a) and formula
(I) outside the monomer (b) also include selected from following one or more of monomers (c) monomer mixture polymerize and
Obtain：
- 2- acrylamido -2- methyl propane sulfonic acids (AMPS)；
- vinylsulfonate, particularly SSS；
- amine；
- the ester containing hydroxyl, such as hydroxyethyl methacrylate (HEMA), hydroxy-ethyl acrylate, hydroxy propyl methacrylate and
Hydroxypropyl acrylate；
- polyalkene glycol acrylate phosphate or aklylene glycol methacrylate phosphate, particularly Ethylene Glycol Methyl
Acrylate phosphate or ethylene glycol acrylate phosphate；
- acrylamide or Methacrylamide；
- phosphonic acid monomer, such as alkyl vinyl phosphonate ester and phosphonate ester；
The macromonomer of-lower formula (VI)：
Ra–[(EO)q–(PO)r–(BO)s]–Ra’ (VI)
Wherein：
[(EO)q-(PO)r-(BO)s] represent by the alcoxyl selected from ethoxy unit EO, propoxy unit PO and butoxyl unit BO
Base unit block, alternately or it is randomly distributed and constitute poly-alkoxyl chain；
Q, r and s represent 0 or 1 to 250 integer independently of one another, and m, n and p summation are 10 to 250；
RaRepresent the group of the mixture selected from acrylate, methacrylate and these esters；With
Ra' represent hydrogen or the alkyl containing 1 to 4 carbon atom；
The hydrophobic monomer of-lower formula (VII)：
Rb–[(EO)t–(PO)u–(BO)v]–Rb’ (VII)
Wherein：
[(EO)t-(PO)u-(BO)v] represent by the alcoxyl selected from ethoxy unit EO, propoxy unit PO and butoxyl unit BO
Base unit block, alternately or it is randomly distributed and constitute poly-alkoxyl chain；
T, u and v represent 0 or 1 to 250 integer independently of one another, and m, n and p summation are 10 to 250；
RbRepresent the group of the mixture selected from acrylate, methacrylate and these esters；With
Rb' represent the alkyl containing 8 to 40 carbon atoms；With
- cross-linking monomer.
11. copolymer according to any one of the preceding claims, it is mixed by using the monomer formed by following components
Compound is polymerize and obtained：
- one or more anionic monomer (a), particularly as limited according to any one of claim 1,8 and 9；With
The monomer (b) of-one or more formula (I), particularly as limited according to any one of claim 1 to 7.
12. a kind of hydraulic-composition for including at least one copolymer limited according to any one of claim 1 to 11.
13. the composition according to claim 12, it includes the 0.05 weight % relative to the composition total weight
To 3 weight %, particularly 0.25 weight % to 2.5 weight % one kind limited according to any one of claim 1 to 11
Or more plant copolymer.
14. the copolymer limited according to any one of claim 1 to 11 is used as the purposes of water reducer in hydraulic-composition.
15. a kind of water reducer for hydraulic-composition, its include according to any one of claim 1 to 11 limited to
A kind of few copolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1552129A FR3033794B1 (en) | 2015-03-16 | 2015-03-16 | NOVEL COPOLYMER AS A WATER-REDUCING AGENT IN A HYDRAULIC COMPOSITION |
| FR1552129 | 2015-03-16 | ||
| PCT/FR2016/050568 WO2016146933A1 (en) | 2015-03-16 | 2016-03-15 | Novel copolymer as a water-reducing agent in a hydraulic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107207678A true CN107207678A (en) | 2017-09-26 |
Family
ID=53177641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680008058.8A Pending CN107207678A (en) | 2015-03-16 | 2016-03-15 | It is used as the new copolymer of water reducer in hydraulic-composition |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP3271306A1 (en) |
| JP (1) | JP2018509489A (en) |
| KR (1) | KR20170129690A (en) |
| CN (1) | CN107207678A (en) |
| BR (1) | BR112017015297A2 (en) |
| CA (1) | CA2975948A1 (en) |
| FR (1) | FR3033794B1 (en) |
| MX (1) | MX2017011453A (en) |
| MY (1) | MY181028A (en) |
| SG (1) | SG11201705679PA (en) |
| WO (1) | WO2016146933A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1345636A (en) * | 1962-10-13 | 1963-12-13 | Device allowing the instant destruction of concrete runways | |
| CN113980199B (en) * | 2021-11-10 | 2023-07-04 | 广西红墙新材料有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
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| US6211317B1 (en) * | 1997-08-01 | 2001-04-03 | Swk Bauchemie Gmbh | Copolymers based on unsaturated dicarboxylic acid derivatives and oxyalkylene glycol alkenyl ethers |
| KR100860470B1 (en) * | 2007-06-04 | 2008-09-25 | 주식회사 엘지화학 | Cement admixture and cement composition comprising the same |
| CN101700964A (en) * | 2009-11-26 | 2010-05-05 | 辽宁科隆精细化工股份有限公司 | Water reducing agent, preparation method thereof and maleic acid mono alkyl ester polyether |
| CN102140018A (en) * | 2010-11-24 | 2011-08-03 | 辽宁奥克化学股份有限公司 | Concrete polycarboxylate water reducer and preparation method thereof |
| JP4968500B2 (en) * | 2005-03-31 | 2012-07-04 | 日油株式会社 | Strength improver for cement, aqueous solution of polycarboxylic acid copolymer for cement admixture, and cement composition |
| CN103965460A (en) * | 2014-05-20 | 2014-08-06 | 武汉理工大学 | Polycarboxylate-type water reducing agent |
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| US4258790A (en) | 1979-01-24 | 1981-03-31 | The Western Company Of North America | Well cementing method using low fluid-loss cement slurry |
| JPS57202311A (en) * | 1981-06-05 | 1982-12-11 | Nippon Shokubai Kagaku Kogyo Co Ltd | Novel block copolymer, its preparation and its use |
| GB9607570D0 (en) | 1996-04-12 | 1996-06-12 | Sandoz Ltd | Improvements in or relating to organic compounds |
| JPH11106247A (en) * | 1997-09-30 | 1999-04-20 | Sanyo Chem Ind Ltd | Dispersant for cement |
| SG101990A1 (en) | 2000-08-11 | 2004-02-27 | Nippon Catalytic Chem Ind | Cement dispersant and cement composition comprising this |
| JP5215663B2 (en) | 2004-09-09 | 2013-06-19 | 株式会社日本触媒 | Copolymers and dispersants |
| JP5306040B2 (en) * | 2008-05-15 | 2013-10-02 | 株式会社日本触媒 | Copolymer composition for cement admixture |
| JP2012071997A (en) * | 2010-09-28 | 2012-04-12 | Sanyo Chem Ind Ltd | Monomer for cement dispersant |
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-
2015
- 2015-03-16 FR FR1552129A patent/FR3033794B1/en active Active
-
2016
- 2016-03-15 EP EP16715014.3A patent/EP3271306A1/en active Pending
- 2016-03-15 CN CN201680008058.8A patent/CN107207678A/en active Pending
- 2016-03-15 WO PCT/FR2016/050568 patent/WO2016146933A1/en active Application Filing
- 2016-03-15 MY MYPI2017702590A patent/MY181028A/en unknown
- 2016-03-15 JP JP2017536922A patent/JP2018509489A/en active Pending
- 2016-03-15 MX MX2017011453A patent/MX2017011453A/en unknown
- 2016-03-15 CA CA2975948A patent/CA2975948A1/en not_active Abandoned
- 2016-03-15 SG SG11201705679PA patent/SG11201705679PA/en unknown
- 2016-03-15 KR KR1020177021925A patent/KR20170129690A/en not_active Application Discontinuation
- 2016-03-15 BR BR112017015297A patent/BR112017015297A2/en not_active Application Discontinuation
Patent Citations (6)
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| US6211317B1 (en) * | 1997-08-01 | 2001-04-03 | Swk Bauchemie Gmbh | Copolymers based on unsaturated dicarboxylic acid derivatives and oxyalkylene glycol alkenyl ethers |
| JP4968500B2 (en) * | 2005-03-31 | 2012-07-04 | 日油株式会社 | Strength improver for cement, aqueous solution of polycarboxylic acid copolymer for cement admixture, and cement composition |
| KR100860470B1 (en) * | 2007-06-04 | 2008-09-25 | 주식회사 엘지화학 | Cement admixture and cement composition comprising the same |
| CN101700964A (en) * | 2009-11-26 | 2010-05-05 | 辽宁科隆精细化工股份有限公司 | Water reducing agent, preparation method thereof and maleic acid mono alkyl ester polyether |
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| CN103965460A (en) * | 2014-05-20 | 2014-08-06 | 武汉理工大学 | Polycarboxylate-type water reducing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| MY181028A (en) | 2020-12-16 |
| KR20170129690A (en) | 2017-11-27 |
| FR3033794A1 (en) | 2016-09-23 |
| SG11201705679PA (en) | 2017-08-30 |
| WO2016146933A1 (en) | 2016-09-22 |
| BR112017015297A2 (en) | 2018-01-09 |
| MX2017011453A (en) | 2018-06-19 |
| CA2975948A1 (en) | 2016-09-22 |
| FR3033794B1 (en) | 2017-03-10 |
| JP2018509489A (en) | 2018-04-05 |
| EP3271306A1 (en) | 2018-01-24 |
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