CN101370747B - Dispersant for hydraulic composition - Google Patents
Dispersant for hydraulic composition Download PDFInfo
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- CN101370747B CN101370747B CN2007800025011A CN200780002501A CN101370747B CN 101370747 B CN101370747 B CN 101370747B CN 2007800025011 A CN2007800025011 A CN 2007800025011A CN 200780002501 A CN200780002501 A CN 200780002501A CN 101370747 B CN101370747 B CN 101370747B
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Abstract
Disclosed is a dispersing agent for hydraulic compositions which contains a polymer that is obtained by copolymerizing a specific monomer (1) such as an ethylene unsaturated carboxylic acid derivative having a polyoxyalkylene group, a phosphate monoester monomer (2), a phosphate diester monomer (3) and an unsaturated carboxylic acid monomer (4) at a pH of 7 or less.
Description
Technical field
The present invention relates to dispersant for hydraulic composition and hydraulic-composition.
Background technology
Hydraulic-composition is with there being the mobile effective material that is called as high-performance water reducing agent of giving in the mixed agent.As its representative, naphthalene sulfonic acidformaldehyde condensation product salt (naphthalene class), trimeric cyanamide sulfonic formaldehyde condensation compound salt (melamine class) are arranged, have the polycarboxylic acid of polyoxyalkylene chain etc.But, usually when using cement dispersants to prepare the concrete of high diminishing, exist slump-loss significantly, problems such as operability reduction such as fillibility and application property.
Therefore, the scheme that all the time proposes is to use as cement dispersants himself having the water-soluble ethylene base co-polymer that prevents the slump-loss performance.
And then, in use in the height ratio such as heat portland cement or low-heat portland cement special cement (with cement composition C
2The cement that S has improved) and cooperated under the concrete situation that the slag cement of blast-furnace slag prepares as hydraulic powder, sometimes owing to having reduced the addition that is used to obtain the cement dispersants that required flowability uses, thereby the slump degree of mobilization reduces as time passes.
And then strong concrete is compared with the concrete of regular tenacity (common intensity), owing to it is to form to mix than (following table is shown water/cement ratio) less cooperation according to water/hydraulic powder to make, therefore has problems such as concrete viscosity height.
For the problem that this viscosity increases,,, concrete viscosity expected thereby reducing the higher additive of effect even polycarboxylic acids dehydragent also fails fully to solve.
For such background, disclosing ethylenic copolymer with long oxyalkylene group of the oxyalkylene group that contains high chain length and short chain and specific monomer among the JP-A11-157897 and serve as must viscosity reduction property composition, strong concrete and the mixed agent of the restraining effect excellence of the delay of condensing.
In addition, proposed among the JP-A2000-327386 that for example what can both show the cement dispersion agent of excellent flowability and high dispersive effect and rapid coagulation for the proportioning that obtains water no matter, used to have the monoesters or the monoether of polyalkylene glycol chain and have unsaturated link(age) and the polymkeric substance of the monomer of phosphate formation.
In addition, the WO-A2006/006732 that announced on January 17th, 2006 discloses polymkeric substance and the hydraulic-composition purposes thereof that is made by 3 kinds of monomers.
Summary of the invention
The present invention relates to contain with the monomer 4 (to call monomer 4 in the following text) of the monomer 3 (to call monomer 3 in the following text) of the monomer 2 (to call monomer 2 in the following text) of the monomer 1 (to call monomer 1 in the following text) of following general formula (1) expression, following general formula (2) expression, following general formula (3) expression and following general formula (4) expression is the dispersant for hydraulic composition that carries out the polymkeric substance that copolymerization obtains below 7 at pH, wherein, the ratio Mw/Mn of weight-average molecular weight of polymkeric substance (Mw) and number-average molecular weight (Mn) is 1.0～2.6.
(in the formula, R
1, R
2Represent hydrogen atom or methyl respectively, R
3The expression hydrogen atom or-(CH
2)
q(CO)
pO (AO)
rR
4, AO represents that carbonatoms is 2～4 oxyalkylene group or Styrene oxide 98min. base, and p is 0 or 1 number, and q is 0～2 number, and p and q are not 0 simultaneously, r is the average addition mole number of AO, is 3～300 number, R
4Expression hydrogen atom or carbonatoms are 1～18 alkyl.)
(in the formula, R
11Expression hydrogen atom or methyl, R
12The expression carbonatoms is 2～12 alkylidene group, and m1 is 1～30 number, M
3, M
4Represent hydrogen atom, basic metal or alkaline-earth metal respectively.)
(in the formula, R
13, R
15Represent hydrogen atom or methyl respectively, R
14, R
16Represent that respectively carbonatoms is 2～12 alkylidene group, m2, m3 are respectively 1～30 number, M
5Expression hydrogen atom, basic metal or alkaline-earth metal.)
(in the formula, R
17～R
19Be respectively hydrogen atom, methyl or (CH
2)
sCOOM
7, (CH
2)
sCOOM
7Also can with COOM
6Or other (CH
2)
sCOOM
7Form acid anhydride, in this case, the M of these groups
6, M
7Do not exist.S represents 0～2 number.M
6, M
7Represent hydrogen atom, basic metal, alkaline-earth metal, ammonium, alkyl ammonium group, substituted alkyl ammonium, alkyl, hydroxyalkyl or alkenyl respectively.)
The present invention and then the manufacture method of phosphate-based polymer is provided, the monomer 4 of the monomer 2 of its monomer 1 with above-mentioned general formula (1) expression, above-mentioned general formula (2) expression, the monomer 3 of above-mentioned general formula (3) expression and above-mentioned general formula (4) expression is to carry out copolymerization below 7 in the presence of chain-transfer agent, at pH.
In addition, the invention provides above-mentioned polymkeric substance or the dispersant for hydraulic composition purposes of the polymkeric substance that obtains with above-mentioned manufacture method.
Embodiment
In the hydraulic-compositions such as concrete in superstrength zone, for the polymkeric substance of JP-A11-157897 or JP-A2000-327386, also expectation can further improve its mobile and viscosity reduction.In addition, from the viewpoint of the versatility that enlarges materials such as cement or aggregate, also expectation can be used the polymkeric substance that is different from the JP-A11-157897 structure.
In the recent period, be in the hydraulic-composition of representative with the concrete, various cement is used, and is not only the different cement of mineral composition, special cement or cooperated the special cement of the slag cement and so on of blast-furnace slag also to be used in the height ratios such as moderate-heat portland cement or low-heat portland cement.In addition, water in the concrete/hydraulic powder is than also expanding scope widely to, especially, surpass the concrete of the so-called general area of above-mentioned scope, require characteristic also inequality than the concrete and the water/hydraulic powder ratio that are the so-called high intensity region of 20～35 weight % for water/hydraulic powder.And then, consider from the manufacturers of hydraulic-composition, according to form, the difference of material uses different dispersion agents, not only makes very loaded down with trivial detailsly, also has to be provided with jar (every kind of needs 2～10m of multiple various dispersion agents in the land used of manufacturers
3Jar), from such background, the dispersion agent that uses in the hydraulic-composition also by expectation can at form so widely, the hydraulic-composition of material and show desired effect separately fully.
At such requirement, consider the characteristic of added ingredients, think that can make up multiple one-tenth assigns to make up dispersion agent or the mixed agent that hydraulic-composition is used.At this moment, think by with the composition (initial stage dispersion component) of initial stage dispersing property excellence, dispersedly keep the composition (disperseing to keep composition) of excellent performance and the composition combinations such as (delay compositions) that brings the appropriateness sclerosis to postpone, can balance obtain dispersiveness, flowability well, the effect of giving of the retentivity that flows, but the mixed agent of JP-A11-157897, JP-A2000-327386 can show effect of sufficient on purposes from this point of view hardly.
The invention provides the dispersant for hydraulic composition that shows the effect of dispersiveness, flowability, the retentivity excellence that flows at the hydraulic-composition of extensive composition, material.
In addition, the present invention relates to following hydraulic-composition, it comprises dispersant for hydraulic composition, hydraulic powder and the water of the invention described above, wherein, hydraulic powder be selected from ordinary Portland cement, moderate-heat portland cement, low-heat portland cement and the blast furnace slag cement more than at least a kind.
In addition, the present invention relates to following hydraulic-composition, it contains dispersant for hydraulic composition, hydraulic powder, fine aggregate, coarse aggregate and the water of the invention described above, wherein, water/hydraulic powder ratio is 20～60 weight %, and the unit water yield is 120～185kg/m
3
According to the present invention, can provide the dispersant for hydraulic composition that all shows the effect of dispersiveness, flowability, the retentivity excellence that flows at the hydraulic-composition of extensive composition, material.
Polymkeric substance of the present invention is as must composition and be to carry out the polymkeric substance that copolymerization obtains below 7 at pH with the monomer 4 of the monomer 3 of the monomer 2 of the monomer 1 of above-mentioned general formula (1) expression, above-mentioned general formula (2) expression, above-mentioned general formula (3) expression and above-mentioned general formula (4) expression.The phosphate of inferring the carboxyl import to these general formulas (4) in the polymkeric substance and general formula (2), (3) thus plays a role as the adsorption group to hydraulic powder, and the oxyalkylene group of general formula (1) plays a role as the repulsion group between the hydraulic powder particle.
About the characterization of adsorption to hydraulic powder of carboxyl and phosphate, though still indeterminate, be presumed as follows.
Usually, cement dispersants forms by showing dispersed " initial stage dispersion component " immediately and show dispersed " disperseing to keep composition " cooperation again through certain hour after mixing after mixing.Existing polycarboxylic acid dispersion agent is to change the initial stage dispersion component and disperse to keep the cooperation of composition recently to distinguish use according to forming (water cement ratio) or material (cement kind).That is, need more ordinary Portland cement or strong concrete for addition, more next corresponding by making the initial stage dispersion component, for special cement (C in the less relatively slag cement of addition, the height ratio
2S is more) or the common intensity concrete, disperse to keep the more next dispersion retentivity that satisfies of composition by making.According to such composition or material, because the addition change needs to distinguish the use cement dispersants.
If the variable of addition is considered according to the cement kind by burning till, the chemical ingredients of cement comprises tricalcium silicate (C
3S), Dicalcium Phosphate (Feed Grade) (C
2S), tricalcium aluminate (C
3A), tetracalcium aluminoferrite (C
4Compound such as AF).The initial stage dispersion component of polycarboxylic acid dispersion agent has the C more to content in the ordinary Portland cement
3A produces the trend of specific adsorption.Therefore, if keep the cooperation ratio of composition according to C such as special cement in slag cement or the height ratio initial stage dispersion component and dispersion
3The less cement of A carries out optimization and the polycarboxylic acid dispersion agent that makes is used for ordinary Portland cement, then because the initial stage dispersion component of polycarboxylic acid dispersion agent is adsorbed in the violent C of initial stage hydration reaction specifically
3A, several minutes stage of a great deal of of initial stage dispersion component hydration in the early stage is disappearance (dispersion agent is embedded in the hydrate) just, can not get the initial stage flowability and show mobile trend as time passes (for increasing the situation that addition comes performance initial stage flowability so have by disperseing to keep composition, disperse to keep composition to become too much, show bigger flowing as time passes).Otherwise, keeping the cooperation ratio of composition to carry out under the optimized situation initial stage dispersion component and dispersion according to ordinary Portland cement, for special cement in slag cement or the height ratio, addition tails off, thereby causes obtaining flowing the maintenance effect.
On the other hand, compare with carboxyl, phosphate does not have special adsorptivity to cement minerals, but because therefore water-soluble reduction can be subjected to the influence of salt concn sometimes along with the cement hydration reaction.That is, for the significant C of initial stage hydration reaction
3The ordinary Portland cement that A content is more has the trend that salt concn raises, rate of adsorption accelerates in the water, for C
3Special cement in slag cement that A is less or the height ratio has the slack-off trend of rate of adsorption.
Therefore infer,, can show desired effect separately fully at the hydraulic-composition of extensive composition, material by containing different carboxyl of this characterization of adsorption and phosphate and carrying out optimization.
[monomer 1]
For monomer 1, the R in the general formula (1)
1, R
2Be respectively hydrogen atom or methyl.R
3For hydrogen atom or-(CH
2)
q(CO)
pO (AO)
rR
4, preferred hydrogen atom.As the alkenyl of general formula (1), can list allyl group, methylallyl etc.P is 0 o'clock, and AO is (CH
2)
qAnd ehter bond, p is 1 o'clock, AO is an ester bond.Q is 0～2, preferred 0 or 1, more preferably 0.P and q are not 0 simultaneously.AO represents that carbonatoms is 2～4 oxyalkylene group or Styrene oxide 98min. base, it is 2～4 oxyalkylene group that AO is preferably carbonatoms, more preferably contain oxyethylene group (to call the EO yl in the following text), the EO base is preferably 70 moles more than the %, more preferably 80 moles more than the %, further preferred 90 moles more than the %, especially preferred all AO are the EO base.R is the average addition mole number of AO, is 3～300 number, from polymkeric substance the dispersiveness of hydraulic-composition and viscosity is lowered the aspect of effect, is 3～300, and is preferred 4～120, more preferably 4～80, further preferred 4～50, further preferred 4～30.In addition, because AO difference in average r the repeating unit, therefore also can comprise mixing of random addition or block addition or both.For example, AO also can contain oxypropylene group etc. except the EO base.
R
4For hydrogen atom or carbonatoms are 1～18 alkyl, more preferably 1～12, further preferred 1～4, further preferred 1,2 alkyl, and then more preferably methyl.
As monomer 1, preferably use (partly) carboxylate that methoxy poly (ethylene glycol), methoxyl group polypropylene glycol, methoxyl group polytetramethylene glycol, methoxyl group polyphenyl form for the polyalkylene glycol of end alkyls such as ethylene glycol, oxyethyl group polyethylene polypropylene glycol envelope chain and (methyl) vinylformic acid, toxilic acid, with the etherate of (methyl) vinyl carbinol formation and on (methyl) vinylformic acid, toxilic acid, (methyl) vinyl carbinol the addition carbonatoms be the affixture of 2～4 epoxy alkane.In addition, (methyl) vinylformic acid refers to vinylformic acid and/or methacrylic acid, and (methyl) allyl group refers to allyl group and/or methylallyl (following identical).
Alkoxyl group more preferably, and then the carboxylate that forms of methoxy poly (ethylene glycol) and (methyl) vinylformic acid more preferably.Specifically can list ω-methoxyl group polyoxyalkylene methacrylic ester, ω-methoxyl group polyoxyalkylene acrylate etc., more preferably ω-methoxyl group polyoxyalkylene methacrylic ester.
The monomer 1 that uses in the manufacturing of polymkeric substance of the present invention for example can prepare by alkoxyl group polyalkylene glycol and (methyl) acrylic acid esterification.Unreacted (methyl) vinylformic acid of this carboxylate can be used as monomer 4.From the inequality of the amount that reduces monomer 4 to make necessary addition constant viewpoint under the situation that is used for the concrete dispersion agent, it is below the 5 weight % with respect to monomer 1 preferably that unreacted (methyl) vinylformic acid of this carboxylate converts with acid type, more preferably below the 3 weight %, further below the preferred 1.5 weight %, below the further preferred 1 weight %.The method of residual (methyl) acrylic acid amount can list distillation, steaming baking, solvent extraction etc. during as the manufacturing that reduces monomer 1.
[monomer 2]
For monomer 2, in the general formula (2), R
11Be hydrogen atom or methyl, R
12It for carbonatoms 2～12 alkylidene group.M1 is 1～30 number, M
3, M
4Be respectively hydrogen atom, basic metal or alkaline-earth metal.M1 in the general formula (2) is preferably 1～20, and more preferably 1～10, further preferred 1～5.
Can list the phosphate monoester of organic hydroxy compounds particularly.Specifically can list polyalkylene glycol list (methyl) acrylate acid phosphoric acid ester etc.For example, can list mono phosphoric acid ester-[(2-hydroxyethyl) methacrylic acid] ester, mono phosphoric acid ester-[(2-hydroxyethyl) acrylate] etc.Wherein, from the easiness of manufacturing and the viewpoint of product quality stability, preferably phosphoric acid list-[(2-hydroxyethyl) methacrylic acid] ester.In addition, also can be an alkali metal salt, alkali earth metal salt, ammonium salt, alkylammonium salt etc. of these compounds.
[monomer 3]
For monomer 3, in the general formula (3), R
13, R
15Be respectively hydrogen atom or methyl, R
14, R
16Be respectively carbonatoms and be 2～12 alkylidene group.M2, m3 are respectively 1～30 number, M
5Be hydrogen atom, basic metal or alkaline-earth metal.M2, m3 in the general formula (3) preferably are respectively 1～20, and more preferably 1～10, further preferred 1～5.
Can list the phosphodiester of organic hydroxy compounds particularly.Specifically can list polyalkylene glycol two (methyl) acrylate acid phosphatase diester etc.For example, can list di(2-ethylhexyl)phosphate-[(2-hydroxyethyl) methacrylic acid] ester, di(2-ethylhexyl)phosphate-[(2-hydroxyethyl) vinylformic acid] ester etc.Wherein, from the easiness of manufacturing and the viewpoint of product quality stability, preferably phosphoric acid two-[(2-hydroxyethyl) methacrylic acid] ester.In addition, also can be an alkali metal salt, alkali earth metal salt, ammonium salt, alkylammonium salt etc. of these compounds.
Monomer 2 and 3 can be used as the mix monomer that contains monomer 2 and monomer 3 and uses.In addition, as monomer 2 and monomer 3, the organic hydroxy compounds that also can use general formula (5) expression reacts with phosphoric acid agent and the phosphoric acid ester that obtains.
The mix monomer that contains monomer 2 and monomer 3 for example also can be used as the resultant of reaction that the organic hydroxy compounds of general formula (5) expression and phosphoric acid agent feed ratio is according to the rules reacted and obtain and makes.
(in the formula, R
20Expression hydrogen atom or methyl, R
21The expression carbonatoms is 2～12 alkylidene group, and m4 represents 1～30 number.)
M4 in the general formula (5) is preferably 1～20, and more preferably 1～10, further preferred 1～5.
As phosphoric acid agent, preferred ortho-phosphoric acid, Vanadium Pentoxide in FLAKES (phosphoric anhydride), Tripyrophosphoric acid, phosphoryl chloride etc., preferred ortho-phosphoric acid, Vanadium Pentoxide in FLAKES.These may be used alone, two or more kinds can also be used in combination.The amount of the phosphoric acid agent when organic hydroxy compounds and phosphoric acid agent reaction can determine according to the composition of target phosphoric acid ester in good time.
The mixture of for example making mono phosphoric acid ester-[(2-hydroxyethyl) methacrylic acid] ester and di(2-ethylhexyl)phosphate-[(2-hydroxyethyl) methacrylic acid] ester can pass through technique known (for example JP-A57-180618) and come synthetic during as phosphoric acid ester.
As the mix monomer that contains monomer 2 and monomer 3, can use the commercially available product that contains monoesters body and diester body, for example, can obtain PHOSMER M, PHOSMER PE, PHOSMER P (UNICHEMICAL), JAMP 514, JAMP 514P, JMP 100 (being the north of the city chemistry), LIGHT-ESTER P-1M, LIGHT-ACRYLATE P-1A (being common prosperity society chemistry), MR200 (big eight chemistry), KAYAMER (Japanese chemical drug), glycolmethacrylate phosphoric acid ester (Aldrich reagent) etc.
Monomer the 2, the 3rd has the monomeric Phosphation thing of unsaturated link(age) and hydroxyl, has confirmed to contain in above-mentioned commercially available product or resultant of reaction the compound except that monoesters body (monomer 2) and diester body (monomer 3).These other compounds think mix polymerizability is arranged, the compound of non-polymerization, but can directly use such mixture (mix monomer) among the present invention.
[monomer 4]
For monomer 4, in the general formula (4), R
17～R
19Be respectively hydrogen atom, methyl or (CH
2)
sCOOM
7, (CH
2)
sCOOM
7Also can with COOM
6Or other (CH
2)
sCOOM
7Form acid anhydride.In this case, the M of these groups
6, M
7Do not exist.S represents 0～2 number.R
17Be preferably hydrogen atom, R
18Be preferably methyl.R
19Be preferably hydrogen atom or (CH
2)
sCOOM
7
M
6, M
7Be respectively hydrogen atom, basic metal, alkaline-earth metal, ammonium, alkyl ammonium group, substituted alkyl ammonium, alkyl, hydroxyalkyl or alkenyl.M
6, M
7Be preferably hydrogen atom, basic metal respectively.
Can list dicarboxylic monomers such as monocarboxylic acid class monomer, toxilic acid, methylene-succinic acid, fumaric acid such as (methyl) vinylformic acid, Ba Dousuan or their acid anhydrides or salt (for example an alkali metal salt, alkali earth metal salt, ammonium salt, hydroxyl can, trialkyl (carbonatoms be 2～8) ammonium salt single, double) or ester particularly by metathetical, preferably (methyl) vinylformic acid, toxilic acid, maleic anhydride, more preferably (methyl) vinylformic acid or their an alkali metal salt.In addition, (methyl) vinylformic acid refers to vinylformic acid and/or methacrylic acid (following identical).
Polymkeric substance of the present invention is for being to carry out phosphate-carboxyl composition polymer that copolymerization obtains below 7 with monomer 1, monomer 2, monomer 3 and monomer 4 at pH.The also preferred mix monomer that contains monomer 2 and monomer 3 that uses.
Monomer 1,2,3 and 4 preferred difference also can be used aforesaid commercially available product or resultant of reaction as previously mentioned.
During monomer copolymerization, in whole monomers that polymerization is used, the ratio of monomer 1 is preferably 60～98 weight %, more preferably 70～95 weight %, further preferred 70～90 weight %.The total ratio of monomer 2 and monomer 3 is preferably 1～39 weight %, more preferably 2～28 weight %, more preferably 5～25 weight %.The ratio of monomer 4 is preferably 1～39 weight %, more preferably 1～28 weight %, more preferably 1～15 weight %.
In addition, monomer 1 and preferred (monomer 1)/(monomer 2+ monomer 3+ monomer 4)=5/95～95/5 of the mol ratio of monomer 2,3 and monomer 4, more preferably 10/90～90/10.In addition, preferred (monomer 2+ monomer 3)/monomer 4=5/95～95/5 of the mol ratio of monomer 2,3 and monomer 4, more preferably 10/90～90/10.In addition, among the present invention,, be based on the acid type compound and calculate weight ratio, weight %, mol ratio or mole % (following identical) for monomer 2 and monomer 3, monomer 4.
In addition, in the manufacturing of polymkeric substance, in the whole monomers that use in the reaction, the ratio of monomer 3 is preferably 1～15 weight %, and more preferably 1～12 weight % further is 2～10 weight %, further is preferably 3～6 weight %.
3 pairs of polymkeric substance that obtain of monomer are given branched structure.Polymkeric substance of the present invention by have the appropriateness branched structure, in the time of on being adsorbed on hydraulic powder, the area that can reduce on hydraulic powder, to occupy.Therefore, the polymkeric substance of greater amt can be adsorbed on the hydraulic powder, in specified range and molecular weight distribution when narrow, the polymkeric substance of greater amt is adsorbed on the hydraulic powder in the value of Mw/Mn described later.Consequently show excellent dispersiveness, flowability and mobile retentivity.
In addition, mol ratio preferred monomers 2/ monomer 3=99/1～4/96 of monomer 2 and monomer 3, more preferably 99/1～5/95.
From suppressing the viewpoint of gelation, the pH that preferably makes the monomer solution that contains monomer 37 is used for reaction to get off.
Below, from gelation suppress, the viewpoint of the functional design of the adjustment of suitable molecular weight and dispersant for hydraulic composition illustrates preferred creating conditions.From this viewpoint, when copolymerization, use total mole number with respect to monomer 1,2,3,4 to be preferably 4 moles more than the %, more preferably 6 moles more than the %, 8 moles of chain-transfer agents more than the % more preferably.In addition, the upper limit of chain-transfer agent usage quantity can be preferably with respect to the total mole number of monomer 1,2,3,4 at 100 moles below the %, more preferably 60 moles below the %, further preferred 30 moles below the %, further preferred 15 moles below the %.Preferred 4～60 moles of %, more preferably 6～30 moles of %, further preferred 8～15 moles of %.
The reactivity of monomer 2,3,4 preferably with more than 60%, more preferably more than 70%, more preferably more than 80%, further be preferably more than 90% and then more preferably be that target is carried out more than 95%, can go out to send the usage quantity of selecting chain-transfer agent from this viewpoint.Herein, the reactivity of monomer 2,3,4 is calculated according to following formula.
Q: reaction finishes the ethylenic unsaturated link(age) of monomer 2, monomer 3 and monomer 4 in the afterreaction system with respect to the R that derives from monomer 1
4Ratio
P: the ethylenic unsaturated link(age) of monomer 2, monomer 3 and monomer 4 during the reaction beginning in the reaction system is with respect to the R that derives from monomer 1
4Ratio
The ratio of the ethylenic unsaturated link(age) of the monomer 2,3,4 in the reaction system after in addition, when beginning reaction and reaction finish in the P contained compound (mole %) can be according to following
1The measurement result of H-NMR is calculated.
[
1H-NMR condition]
To be dissolved in the polymkeric substance drying under reduced pressure of water, the concentration of gains with 3～4 weight % is dissolved in the heavy methyl alcohol, measure
1H-NMR.The ratio of ethylenic unsaturated link(age) is measured by the integrated value of 5.5～6.2ppm.In addition,
1H-NMR is determined at that " Mercury 400NMR ", the data point (data point) of using the Varian corporate system are several 42052, measurement range 6410.3Hz, pulse width 4.5 μ s, pulse waiting time 10s, measures under the condition of 25.0 ℃ of temperature and carry out.
In the manufacturing of polymkeric substance, except above-mentioned monomer 1,2,3,4, also can use can copolymerization other monomer.Other monomer as can copolymerization can list allyl sulphonic acid, methallyl sulfonic acid, their arbitrary an alkali metal salts, alkali earth metal salt, ammonium salt or amine salt.In addition, can list acrylic monomers such as vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, also can be any acid anhydrides such as an alkali metal salt, alkali earth metal salt, ammonium salt, amine salt, methyl esters, ethyl ester or maleic anhydride more than a kind in them.And then, can list (methyl) acrylamide, N-methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, 2-(methyl) acrylamide-2-methylsulfonic acid, 2-(methyl) acrylamide-2-ethanesulfonic acid, 2-(methyl) acrylamide-2-propanesulfonic acid, vinylbenzene, styrene sulfonic acid etc.All in the monomer, the total ratio of monomer 1,2,3 is preferably 30～100 moles of %, more preferably 50～100 moles of %, further preferred 75～100 moles of %, and then, more preferably surpass 95 moles of % and smaller or equal to 100 moles of %, further preferred 97～100 moles of %, further preferred 100 moles of %.
The manufacturing of polymkeric substance preferably makes monomer carry out copolymerization in the presence of the chain-transfer agent of specified amount.In addition, also can use can copolymerization other monomer or polymerization starter etc.
Preferred 40～100 ℃ of the temperature of reaction of monomer 1,2,3,4, more preferably 60～90 ℃, (1～1.1atm), more preferably 101.3～106.4kPa (1～1.05atm) in the preferred 101.3～111.5kPa of gauge pressure for reaction pressure.
The pH of reaction system can be as required waits and adjusts with mineral acid (phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid etc.) or NaOH, KOH, trolamine.
Herein, the monomer solution that contains monomer 3 is preferably Aquo System (that is, solvent comprises water) from pH mensuration aspect, also can add the water of necessary amount during non-aqueous system and measure.From the homogeneity of monomer solution, prevent the viewpoint that gelation, rejection reduce, pH is preferably below 7, more preferably 0.1～6, more preferably 0.2～4.5, further be preferably 0.5～3.In addition, also preferably to make pH be that monomer solution below 7 uses to monomer 1.This pH is 20 ℃ of values of measuring down.
Among the present invention, will be in reaction process the pH of reaction soln under 20 ℃ of (during the reaction beginning～when reaction finishes) sampling as the pH in reacting.Preferably the pH in clear and definite reaction begins to react under the condition (monomer ratio, solvent, other one-tenth grade) 7 below.
In addition, if reaction system is non-aqueous system, measure after can in reaction system, adding the water of the amount that can carry out pH mensuration.
In the manufacture method of polymkeric substance,, then under the situation of considering other condition, it has been generally acknowledged that pH in the reaction is also below 7 under following (1), (2) illustrated condition if monomer 1,2,3,4 reacts.
(1) pH that will contain whole monomers 1,2,3,4 is the copolyreaction that monomer solution below 7 is used for monomer 1,2,3,4.
(2) at pH be the copolyreaction of the monomer 1,2,3,4 of beginning below 7.That is, the reaction system that will comprise monomer 1,2,3,4 is adjusted to pH and begins reaction after below 7.
[chain-transfer agent]
Chain-transfer agent is that to have the function that causes chain transfer reaction (free polymer readical of growing up and other molecule react and cause the reaction of moving of free radical activity point) in radical polymerization, be the material that purpose is added with the monomeric transfer of chain.
As chain-transfer agent, can list mercaptan type chain transfer agent, halogenated hydrocarbons chain-transfer agent etc., preferred mercaptan type chain transfer agent.
As mercaptan type chain transfer agent, preferably have-mercaptan type chain transfer agent of SH base, more preferably use general formula HS-R-Eg (in the formula, R represents that carbonatoms is the group in 1～4 hydrocarbon source, E represents-OH ,-COOM ,-COOR ' or-SO
3M group, M are represented hydrogen atom, monovalence metal, divalent metal, ammonium or organic amino group, and R ' expression carbonatoms is 1～10 alkyl, and g represents 1～2 integer.) expression mercaptan type chain transfer agent, for example, can list mercaptoethanol, thioglycerin, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptosuccinic acid, Thiovanic acid monooctyl ester, 3-thiohydracrylic acid monooctyl ester etc., the viewpoint of the chain transfer effect from the copolyreaction that contains monomer 1～3, preferred thiohydracrylic acid, mercaptoethanol, more preferably thiohydracrylic acid.They can use more than a kind or 2 kinds.
As the halogenated hydrocarbons chain-transfer agent, can list tetracol phenixin, carbon tetrabromide etc.
As other chain-transfer agent, can list α-Jia Jibenyixierjuwu, terpinolene, α-terpinene, γ-terpinene, limonene, 2-aminopropane-1-alcohol etc.Chain-transfer agent can use more than a kind or 2 kinds.
[polymerization starter]
In the manufacture method of polymkeric substance, preferably use polymerization starter, especially the usage quantity of preferred polymeric initiator with respect to the total mole number of monomer 1,2,3,4 at 5 moles more than the %, more preferably 7～50 moles of %, further preferred 10～30 moles of %.
As the polymerization starter of water system, can use persulfuric acid ammonium salt or an alkali metal salt or hydrogen peroxide, 2, two (2-amidine propane) dihydrochlorides, 2 of 2 '-azo, water-soluble azo compounds such as two (2-methyl propanamide) dihydrates of 2 '-azo.In addition, also can use promotor and polymerization starter and usefulness such as sodium bisulfite, amine compound.
[solvent]
The manufacturing of polymkeric substance can be implemented by solution polymerization process, as the solvent that at this moment uses, can enumerate water outlet or contain water and the solvent of the water-containing solvent class of methyl alcohol, ethanol, Virahol, acetone, methylethylketone etc.Consider preferably water from property handled and conversion unit.When especially using the solvent of water system, the pH that preferably contains the monomer solution of monomer 3 is below 7, from the viewpoint of the homogeneity (processing) of monomer mixed solution, monomer reaction rate, suppress the crosslinked viewpoint that the burnt body hydrolysis by phosphate compound causes, more preferably be 0.1～6, especially preferably be to be used for reaction 0.2～4 time to carry out copolyreaction at pH at pH.
One example of polymkeric substance manufacture method is shown.The water that adds specified amount in reaction vessel is with inertness gas displacement atmosphere such as nitrogen and intensification.Prepare in advance to be dissolved in the solution that water forms, these two parts of solution were dropped in the reaction vessel with 0.5～5 hour with monomer 1, monomer 2, monomer 3, monomer 4, the chain-transfer agent solution that mixed dissolution forms in water with polymerization starter.At this moment, also each monomer, chain-transfer agent and polymerization starter can be dripped respectively, also monomeric mixing solutions can be joined in advance in the reaction vessel and only drip polymerization starter.Promptly, chain-transfer agent, polymerization starter and other additive can add as additive solution dividually with monomer solution, also can cooperate the back to add with monomer solution, but consider from the viewpoint of polymeric stability, preferably be added in the reaction system as additive solution dividually with monomer solution.Which kind of situation no matter, the preferred pH of solution that contains monomer 3 is below 7.In addition, by sour agent etc. pH is maintained 7 and carry out copolyreaction, preferably carry out the slaking of specified time to get off.In addition, polymerization starter can all drip with monomer simultaneously, also can gradation add, and from reducing the viewpoint of unreacted monomer, preferred gradation is added.For example, preferably in the final whole polymerization starters that use, polymerization starter and monomer with 1/2～2/3 add simultaneously, and remainder finishes to add after 1～2 hour the slaking in back at monomer dropping again.In case of necessity, after slaking finishes, use alkaline agent (sodium hydroxide etc.) to neutralize again, thereby obtain polymkeric substance of the present invention.This Production Example is fit to as the manufacture method of polymer A of the present invention.
The monomer 1,2,3,4 of reaction system and other monomeric total amount that can copolymerization are preferably 5～80 weight %, more preferably 10～65 weight %, 20～50 weight % more preferably.
Polymkeric substance preferable weight-average molecular weight (Mw) is 10,000～100,000.From the viewpoint of performance dispersion effect and viscosity reduction effect, the Mw of this polymer A is more than 10,000, preferred more than 12,000, more preferably 13, more than 000, further preferred more than 14,000, further preferred more than 15,000, quantize from suppressing the crosslinked polymer that causes, the dispersion effect of gelation and aspect of performance and viscosity reduce the viewpoint of effect and set out, the Mw of this polymer A is below 100,000, preferred 95, below 000, more preferably below 90,000, further preferred below 85,000, further preferred 80, below 000, from above-mentioned two viewpoints, the Mw of this polymer A preferred 12,000～950,000, more preferably 13,000～90,000, further preferred 14,000～85,000, further preferred 15,000～80,000, and then more preferably 20,000～60,000, more further preferred 30,000～50,000.Preferably has the Mw in this scope.
Mw/Mn of the present invention is 1.0～2.6.Herein, Mn is a number-average molecular weight.Herein, the value of Mw/Mn is a dispersity, means the approaching more single dispersion of molecular weight distribution near 1 more, departs from 1 (increase) more and means that then molecular weight distribution is wide more.
Reduce the viewpoint of effect from dispersion effect and viscosity, the Mw/Mn of polymkeric substance is preferred 1.0～2.4, and more preferably 1.0～2.2, further preferred 1.0～2.0, further preferred 1.0～1.8.
The bigger of polymkeric substance of the present invention with above-mentioned Mw/Mn value be characterised in that, it is the polymkeric substance that has based on the branched structure of two ester structures of monomer 3, and molecular weight distribution is very narrow.Polymkeric substance of the present invention like this can for example be made by the amount of adjusting chain-transfer agent aptly.When increasing the amount of chain-transfer agent, then the value of Mw/Mn diminishes.
The Mw of polymkeric substance and Mn are to use the gel permeation chromatography (GPC) of following condition to measure.In addition, the Mw of polymkeric substance of the present invention and Mn are based on that the peak of this polymkeric substance calculates.
[GPC condition]
Chromatographic column: G4000PWXL+G2500PWXL (TOSOH)
Elutriant: 0.2M phosphoric acid buffer/CH
3CN=9/1
Flow: 1.0ml/min
Column temperature: 40 ℃
Detect: RI
Sample size: 0.2mg/mL
Reference material: polyoxyethylene glycol converts
In addition, from the viewpoint of dispersed (necessary addition reduction) and viscosity reduction effect, more preferably in the collection of illustrative plates of the molecular weight distribution that expression obtains with the GPC method under the above-mentioned condition, the area of molecular weight more than 100,000 is below 5% of this collection of illustrative plates total area.
＜dispersant for hydraulic composition 〉
From showing viewpoint mobile and viscosity reduction effect, dispersant for hydraulic composition of the present invention is with respect to hydraulic powder, especially cement 100 weight parts, in solid component concentration, preferably with 0.1～5 weight part, more preferably use with the ratio of 0.2～3 weight part.
Dispersant for hydraulic composition of the present invention also can contain other additive (material).For example, can list AE agent such as sodium resinate, saturated or unsaturated fatty acids, hydroxyl sodium stearate, dodecyl sulfate, alkyl benzene sulphonate (ABS) (salt), alkane sulfonate, polyoxyalkylene alkyl (phenyl) ether, polyoxyalkylene alkyl (phenyl) ether sulfuric ester (salt), polyoxyalkylene alkyl (phenyl) ether phosphate (salt), protein material, alkenyl succinic, sulfonated; Pore forming material; Thickening material; Silica sand; The AE water reducer; Hardening accelerator or promotor such as muriates such as soluble calcium salts such as calcium chloride, calcium nitrite, nitrocalcite, Calcium Bromide, calcium iodide, iron(ic) chloride, magnesium chloride etc., vitriol, potassium hydroxide, sodium hydroxide, carbonate, thiosulphate, formic acid (salt), alkanolamine; Whipping agent; Water-resisting agents such as resinous acid (salt), fatty acid ester, grease, organosilicon, paraffin, pitch, wax; Blast-furnace slag; Flowing agent; Defoamers such as dimethyl polysiloxane class, polyalkylene glycol fatty acid class, mineral oils, lipid, oxyalkylene class, alcohols, amides; Foam preventer; Flying dust; Trimeric cyanamide sulfonic formaldehyde condensation compound class, thionamic acid class, the contour performance water reducer of polymaleic acid class; The silicon ash; Rust-preventive agent such as nitrite, phosphoric acid salt, zinc oxide; The water-soluble polymer of the synthetic classes such as reactant that the EO affixture of polyacrylamide, polyoxyethylene glycol, oleyl alcohol or these and vinyl cyclohexene diepoxide form etc.; Polymer emulsions such as (methyl) alkyl acrylate.In all solids composition of concrete dispersion agent of the present invention, the concentration of polymkeric substance is preferably 20～100 weight %, more preferably 20～80 weight %, further preferred 25～70 weight %, further preferred 30～70 weight %.
In addition, polymkeric substance of the present invention also can use separately, but from the viewpoint of further raising retentivity, preferably with above-mentioned " disperseing to keep composition " (to call retention agent in the following text) and use.In this case, preferred polymkeric substance/retention agent of the present invention=20/80～90/10, more preferably 25/75～80/20.As retention agent, unqualified, preferably do not contain monomer 4 and be to carry out the polymkeric substance that copolymerization obtains below 7 at pH monomer 1, monomer 2, monomer 3.
Retention agent is the preparation that is adsorbed on as time passes on the hydraulic powder with the flowability that shows hydraulic-composition.By with polymkeric substance of the present invention and retention agent and usefulness, even the back of mixing is through also keeping the flowability of hydraulic-composition after a while.
With polymkeric substance of the present invention and retention agent and time spent, even mixing afterwards through after a while, hydraulic-composition still has flowability, therefore, for making fresh concrete (still uncured concrete) in factory, and grow, for example be useful under the situation more than 30 minutes to building on-the-spot handling time.
Otherwise, for the situation of in same land used, making concrete product, perhaps also be make fresh concrete but with fresh concrete be transported to build the on-the-spot time short, for example less than under 30 minutes the situation, preferably use polymkeric substance of the present invention separately.
In addition, as mentioned above, guess because polymkeric substance of the present invention is to be adsorbed on during hydration reaction by the initial stage after hydraulic powder and water have just been mixed to show effect of the present invention on the hydraulic powder as the unqualified reason of retention agent, therefore, absorption takes place as time passes and the absorption of the initial stage of the mobile retention agent of performance after the hydraulic powder of polymkeric substance of the present invention and water have just been mixed during hydration reaction does not exert an influence.
From being adsorbed on as time passes on the hydraulic powder and show the viewpoint of the flowability of hydraulic-composition, is the composition that carries out the phosphate-based polymer that copolymerization obtains below 7 for above-mentioned record at pH with monomer 1, monomer 2, monomer 3, in the monomer that in the polymerization of this polymkeric substance, uses, 60～90 moles of % of monomer 1 preferred use, more preferably use 60～85 moles of %, 65～80 moles of % of further preferred use.Monomer 2 and 3 total are preferably used 10～40 moles of %, more preferably use 15～40 moles of %, further preferably use 20～35 moles of %.Monomer 2 and 3 ratio can use and polymer phase of the present invention with mol ratio.
In addition, the also usefulness of the retention agent of polycarboxylic acid dispersion agent is also effective.An example as the retention agent of polycarboxylic acid dispersion agent, can list the polymkeric substance that monomer 1 and monomer 4 is carried out copolymerization and obtain, from being adsorbed on as time passes on the hydraulic powder and show the viewpoint of the flowability of hydraulic-composition, in the monomer that uses in the polymerization of this polymkeric substance, 20～70 moles of % of monomer 1 preferred use, more preferably use 25～60 moles of %, 30～50 moles of % of further preferred use, 30～80 moles of % of monomer 4 preferred uses, more preferably use 40～75 moles of %, 50～70 moles of % of further preferred use.Wherein, from suppressing hydraulic-composition as time passes and the viewpoint that viscosity increases, the preferably retention agent that forms by phosphate-based polymer.
＜hydraulic-composition 〉
Hydraulic-composition as object of the present invention is the hydraulic-composition that contains hydraulic powder and water, and hydraulic powder refers to the powder with hardened rerum natura by hydration reaction, can list cement, gypsum etc.Preferred ordinary Portland cement, than cement such as the special cement in lining, moderate heat cement, short-term strength cement, super-early strength cement, the cement of anti-sulfuric acid, also can be the cement that has added blast-furnace slag, flying dust, silicon ash, stone flour (calcium carbonate powders) etc. in these.In addition, in these powders, add sand, sand and gravel as aggregate (fine aggregate, coarse aggregate) and the hydraulic-composition of finally making is called as mortar, concrete etc. usually respectively.Dispersion agent of the present invention, hydraulic-composition except the field of ready mixed concrete, vibratory concrete product, can also be used for from levelling with, refractory body with, the plaster of Paris with, calcium plaster with, light weight or weight concrete with, AE with, repair with, grouted aggregate concrete with, tremie with, be in the milk and various concrete arbitrary fields such as use with, phase in severe winter with, foundation improvement.
Hydraulic-composition as object of the present invention, especially concrete, its water/hydraulic powder is than [water in the slip and the weight percent of hydraulic powder (weight %), usually be abbreviated as W/P, but be abbreviated as W/C when powder is cement] be preferably below the 65 weight % more preferably 10～60 weight %, further preferred 12～57 weight %, further preferred 15～55 weight %, and then more preferably 20～55 weight %.Particularly the high strength of 20～35 weight % cooperates, and can significantly bring into play the effect of dispersion agent of the present invention for various cement.
From suppressing the viewpoint of cement amount (economy), the every 1m of hydraulic-composition of the present invention
3The water yield, be that the unit water yield is preferably 120～185kg/m
3Particularly, the unit water yield of preferred above-mentioned scope when W/P is 20～60 weight %.
Embodiment
Below put down in writing embodiment, but scope of the present invention is not limited to following embodiment.
Production Example (R-1)
In having the glass reaction vessel (four-hole boiling flask) of agitator, add entry 367g, carry out nitrogen replacement when stirring, in nitrogen atmosphere, be warming up to 80 ℃.(effective constituent is 60.8 weight % with ω-methoxy poly (ethylene glycol) monomethacrylates (the average addition mole number of oxyethane is 23) 426g, moisture is 35 weight %), methacrylic acid 64.2g and 3-thiohydracrylic acid 3.2g mix, to wherein adding 85% phosphoric acid, adjusting pH is 2.0, with gained solution and ammonium persulphate 11.4g be dissolved in the formation of 64g water solution the two dripped with 1.5 hours respectively.After 1 hour the slaking, the solution that ammonium persulphate 5.7g is dissolved in the formation of 32g water dripped with 30 minutes, carried out 1.5 hours slaking afterwards under uniform temp (80 ℃).Slaking finishes the back and drips 32% aqueous sodium hydroxide solution, and being neutralized to pH is 6.0, obtains weight-average molecular weight and be 48000 polymkeric substance R-1.(reactivity is 100%).Monomeric kind, its mole %, weight %, all the weight-average molecular weight and the weight-average molecular weight of the pH the when ratio of monomer 3, reaction in the monomer, the polymkeric substance that obtains are as shown in table 1 with the ratio (Mw/Mn) of number molecular-weight average.
Production Example (R-2)
In having the glass reaction vessel (four-hole boiling flask) of agitator, add entry 352g, carry out nitrogen replacement when stirring, in nitrogen atmosphere, be warming up to 80 ℃.(effective constituent is 60.8 weight % with ω-methoxy poly (ethylene glycol) monomethacrylates (the average addition mole number of oxyethane is 23) 397g, moisture is 35 weight %), the mixture of mono phosphoric acid ester-[(2-hydroxyethyl) methacrylic acid] ester and di(2-ethylhexyl)phosphate-[(2-hydroxyethyl) methacrylic acid] ester is that Phosphation thing (A) 123.4g and 3-thiohydracrylic acid 6.1g mix, gained solution and ammonium persulphate 11.9g are dissolved in solution that 67g water forms, and the two dripped with 1.5 hours respectively.After 1 hour the slaking, the solution that ammonium persulphate 2.6g is dissolved in the formation of 15g water dripped with 30 minutes, carried out 1.5 hours slaking afterwards under uniform temp (80 ℃).Slaking finishes the back and drips 32% aqueous sodium hydroxide solution, and being neutralized to pH is 6.0, obtains weight-average molecular weight and be 36000 polymkeric substance R-2.(reactivity is 99%).
Following the making of Phosphation thing (A) of using in this Production Example: in reaction vessel, add methacrylic acid 2-hydroxyl ethyl ester 200g and 85% phosphoric acid (H
3PO
4) 36.0g, when making temperature be no more than 60 ℃, cooling slowly adds Vanadium Pentoxide in FLAKES (phosphoric anhydride) (P
2O
5) 89.1g, afterwards, temperature of reaction is set in 80 ℃, reacted 6 hours, make after the cooling.In following part Production Example, also used this Phosphation thing (A).
Production Example (A-1)
In having the glass reaction vessel (four-hole boiling flask) of agitator, add entry 346g, carry out nitrogen replacement when stirring, in nitrogen atmosphere, be warming up to 80 ℃.(effective constituent is 60.8 weight % with ω-methoxy poly (ethylene glycol) monomethacrylates (the average addition mole number of oxyethane is 23) 391g, moisture is 35 weight %), the mixture of mono phosphoric acid ester-[(2-hydroxyethyl) methacrylic acid] ester and di(2-ethylhexyl)phosphate-[(2-hydroxyethyl) methacrylic acid] ester is that Phosphation thing (A) 64.9g, methacrylic acid 43.2g and 3-thiohydracrylic acid 4.9g mix, with gained solution and ammonium persulphate 14.6g be dissolved in solution that 83g water forms the two respectively with dropping in 1.5 hours.After 1 hour the slaking, the solution that ammonium persulphate 4.2g is dissolved in the formation of 24g water dripped with 30 minutes, carried out 1.5 hours slaking afterwards under uniform temp (80 ℃).Slaking finishes the back and drips 32% aqueous sodium hydroxide solution, and being neutralized to pH is 6.0, obtains weight-average molecular weight and be 42000 polymer A-1.(reactivity is 100%).
Production Example (A-2)
Polymer A-2 is except the amount of monomer ratio that adopts table 1, and all the other and polymer A-1 are similarly made.
Table 1 has been put down in writing the monomeric charge ratio of above-mentioned Production Example etc. in the lump.
Table 1
Symbolic significance is as follows in the table, and the number in () is the average addition mole number of EO (following identical).
MEPEG-E: ω-methoxy poly (ethylene glycol) monomethacrylates
MAA: methacrylic acid
HEMA-MPE:2-hydroxyethyl meth acrylate phosplate
HEMA-DPE:2-hydroxyethyl meth acrylate bisphosphate
Mw: weight-average molecular weight
Production Example (B-1 and B-2)
Polymer B-1 and B-2 are except the monomer ratio that adopts table 2, and other and polymkeric substance R-2 similarly make.Table 2 has been put down in writing the monomeric charge ratio of this Production Example etc. in the lump.
Table 2
＜test example〉[concrete test]
(1) cement dispersants
Table 1,2 polymkeric substance etc. are used according to the weight ratio of table 4～6, make cement dispersants.Use this cement dispersants, the concrete that cooperates according to table 3 is carried out following test.Its result is shown in table 4～6.In addition, S-1 is sucrose (delayed-action activator).
(2) concrete cooperates
Concrete cooperates as shown in table 3.
Table 3
Materials used in the table 3 is as follows.
W: ion exchanged water
C1: common silicate cement (1: 1 mixture of common silicate cement of Pacific comment Co., Ltd's system and the common silicate cement of Sumitomo Osaka Cement Co., Ltd.'s system)
C2: low-heat portland cement (Pacific comment Co., Ltd's system low-heat portland cement)
S1: fine aggregate, rugged beautiful county youngster produces land sand (density: 2.62g/cm in beautiful prefecture
3)
S2: fine aggregate, Tochigi peace Su Jun produces broken sand (density: 2.62g/cm
3)
S1: fine aggregate, order (density: 2.61g/cm in the sand of mountain is produced prefecture, monarch Tianjin, Chiba county
3)
G: coarse aggregate, Tochigi peace Su Jun produces rubble 2005 (density: 2.70g/cm
3)
(3) concrete preparation
As the blender that uses, pressure twin screw the mixings machine that uses IHI company to make, the concrete capacity is 30 liters, churning time is mixed 10 seconds, adding and was mixed behind the water 90 seconds for empty, thereby has prepared concrete.At this moment, for cooperating I and cooperating II, adjust the addition of dispersion agent (polymer complexes), so that slump degree of mobilization value is 600～680mm in preparation after 30 minutes.For cooperating IH, adjust the addition of cement dispersants, so that the slump after the preparation just is 20～22cm.
In addition, cooperate I and to cooperate the slump degree of mobilization value of II be the mean value of the slump degree of mobilization value measured on maximum value and the direction that intersects vertically at the 1/2 length place that gives this peaked line segment of slump degree of mobilization value.In addition, concrete slump slump test is according to JIS A 1150, except stabbing 5 times with rod is same at each layer, tests similarly that (overall dimension of coarse aggregate (G) is 20mm, concrete temperature is 20～22 ℃, the Packaging Method of sample: be divided into 3 layers of packing).In addition, cooperate the slump value of III to carry out according to slump consistancy test (JIS A 1101).In addition,,, add defoamer,,, add defoamer, so that the bubble train amount is 4.0～5.0 volume % for cooperating III so that the bubble train amount is below the 3.0 volume % for cooperating I and cooperating II about concrete air capacity (JIS A 1128).
(4) concrete evaluation
For having added the as above concrete of the dispersion agent of preparation, measure the flowability (the slump degree of mobilization or the slump) after just stirring and leave standstill after 15 minutes or 30 minutes flowability (the slump degree of mobilization or the slump) after stirring repeatedly with little scoop.The results are shown in Table 4～table 6.Table 4 is for cooperating the result of I (ordinary Portland cement, W/C=30 weight %), and table 5 is for cooperating the result of II (low-heat portland cement, W/C=30 weight %), and table 6 is for cooperating the result of III (ordinary Portland cement, W/C=45 weight %).Cooperate I and II owing to be that strong concrete has been measured the slump degree of mobilization, cooperation III is owing to being that the common intensity concrete has been measured the slump.
Table 4
In the table 4, addition is the weight % (following identical) of dispersion agent (being scaled solids component) with respect to cement weight.
Table 5
Table 6
Test example 1 and 6 has been to use the test of the dispersion agent of polycarboxylic acid polymkeric substance, test example 3 and 8, test example 4 and 9 and test example 5,10 and 11 be to use the test of the dispersion agent of polymkeric substance of the present invention.Whole test examples all and used the phosphoric acid base polymer.
According to the test example of having used polymkeric substance of the present invention as can be known, arbitrary be engaged in firm stirring back, after 15 minutes or the mobility variations after 30 minutes all very little, hydraulic-composition at extensive composition (water cement ratio), material (cement kind) can show desired effect separately fully.On the other hand, according to be ordinary Portland cement and W/C=30 weight % cooperation I (table 4) as can be known, the slump degree of mobilization value after just having stirred in the paralled system of polycarboxylic acid polymkeric substance (test example 1) is little and the trend that increases after 15 minutes arranged.In addition, according to be low-heat portland cement and W/C=30 weight % cooperation II (table 5) as can be known, the slump degree of mobilization value after just having stirred in the test example 7 is little and the trend that increases after 15 minutes arranged.
In addition, polymkeric substance R-2 of the present invention and do not use the weight-average molecular weight of A-2 of monomer 4 and the Mw/Mn value much at one.Cooperate the test example 4 of having used polymkeric substance among the I respectively and the difference of testing the slump degree of mobilization of example 2 after 15 minutes not to have a great difference, but the difference of the slump degree of mobilization after 15 minutes have a great difference in the test example 9 of cooperation II and the test example 7.Thus the result as can be known, polymkeric substance of the present invention for form or the versatility of the hydraulic powder that material is different higher.
Test example 12
Use ω-methylol polyethyleneglycol methacrylic acid (the average addition mole number of oxyethane is 23) as monomer 1, consumption is 40 moles of %, uses methacrylic acid as monomer 4, and consumption is 60 moles of %, (R-1) carries out polymerization according to Production Example, obtains polymer B-3.
Except the polymer B-2 of using polymer B-3 replacement test example 3, similarly estimate.For the hydraulic-composition after mixing 15 minutes, though with test example 3 mutually specific viscosity increase to some extent, infer that the slump degree of mobilization can obtain and test the almost equal result of example 3.
Claims (20)
1. dispersant for hydraulic composition, its monomer 4 that contains with the monomer 3 of the monomer 2 of the monomer 1 of following general formula (1) expression, following general formula (2) expression, following general formula (3) expression and following general formula (4) expression is to carry out the polymkeric substance that copolymerization obtains below 7 at pH, wherein, the weight-average molecular weight Mw of polymkeric substance and the ratio Mw/Mn of number-average molecular weight Mn are 1.0～2.6
In the formula, R
1, R
2Represent hydrogen atom or methyl respectively, R
3The expression hydrogen atom or-(CH
2)
q(CO)
pO (AO)
rR
4, AO represents that carbonatoms is 2～4 oxyalkylene group or Styrene oxide 98min. base, and p is 0 or 1 number, and q is 0～2 number, and p and q are not 0 simultaneously, r is the average addition mole number of AO, is 3～300 number, R
4Expression hydrogen atom or carbonatoms are 1～18 alkyl;
In the formula, R
11Expression hydrogen atom or methyl, R
12The expression carbonatoms is 2～12 alkylidene group, and m1 is 1～30 number, M
3, M
4Represent hydrogen atom, basic metal or alkaline-earth metal respectively;
In the formula, R
13, R
15Represent hydrogen atom or methyl respectively, R
14, R
16Represent that respectively carbonatoms is 2～12 alkylidene group, m2, m3 are respectively 1～30 number, M
5Expression hydrogen atom, basic metal or alkaline-earth metal;
In the formula, R
17～R
19Represent hydrogen atom, methyl or (CH respectively
2)
sCOOM
7, (CH
2)
sCOOM
7Also can with COOM
6Or other (CH
2)
sCOOM
7Form acid anhydride, in this case, the M of these groups
6, M
7Do not exist, s represents 0～2 number, M
6, M
7Represent hydrogen atom, basic metal, alkaline-earth metal, ammonium, alkyl ammonium group, substituted alkyl ammonium, alkyl, hydroxyalkyl or alkenyl respectively.
2. according to the dispersant for hydraulic composition of claim 1 record, wherein, it is that add up to 1～39 weight %, monomer 4 of 60～98 weight %, monomer 2 and monomer 3 is that the ratio of 1～39 weight % is carried out copolymerization and obtained with monomer 1 in the whole monomers that constitute polymkeric substance.
3. according to the dispersant for hydraulic composition of claim 1 or 2 records, wherein, the weight-average molecular weight Mw of polymkeric substance is 15,000～80,000.
4. according to the dispersant for hydraulic composition of claim 1 or 2 records, it further contains retention agent.
5. according to the dispersant for hydraulic composition of claim 3 record, it further contains retention agent.
6. hydraulic-composition, it contains dispersant for hydraulic composition, hydraulic powder and the water of any record of claim 1～5, wherein, hydraulic powder be selected from ordinary Portland cement, moderate-heat portland cement, low-heat portland cement and the blast furnace slag cement more than at least a kind.
7. hydraulic-composition, it contains dispersant for hydraulic composition, hydraulic powder, fine aggregate, coarse aggregate and the water of any record of claim 1～5, wherein, water/hydraulic powder ratio is 10～60 weight %, and the unit water yield is 120～185kg/m
3
8. the manufacture method of a phosphate-based polymer, wherein, the monomer 4 of the monomer 3 of general formula (3) expression of the monomer 2 of general formula (2) expression of the monomer 1 that the general formula (1) of claim 1 record is represented, claim 1 record, claim 1 record and general formula (4) expression that claim 1 is put down in writing is to carry out copolymerization below 7 in the presence of chain-transfer agent, at pH.
9. the manufacture method of phosphate-based polymer of record according to Claim 8, wherein, the ratio Mw/Mn of the weight-average molecular weight Mw of resulting polymers and number-average molecular weight Mn is 1.0～2.6.
10. according to Claim 8 or the manufacture method of phosphate-based polymers of 9 records, wherein, the weight-average molecular weight Mw of resulting polymers is 15,000～80,000.
11. according to Claim 8 or the manufacture method of phosphate-based polymers of 9 records, wherein, chain-transfer agent is a mercaptan type chain transfer agent.
12. according to the manufacture method of the phosphate-based polymer of claim 10 record, wherein, chain-transfer agent is a mercaptan type chain transfer agent.
13. according to Claim 8 or the manufacture method of phosphate-based polymers of 9 records, wherein, in the whole monomers that use in the polymkeric substance, the ratio of monomer 1 is 60～98 weight %, the total ratio of monomer 2 and monomer 3 is 1～39 weight %, and the ratio of monomer 4 is 1～39 weight %.
14. manufacture method according to the phosphate-based polymer of claim 10 record, wherein, in the whole monomers that use in the polymkeric substance, the ratio of monomer 1 is 60～98 weight %, the total ratio of monomer 2 and monomer 3 is 1～39 weight %, and the ratio of monomer 4 is 1～39 weight %.
15. manufacture method according to the phosphate-based polymer of claim 11 record, wherein, in the whole monomers that use in the polymkeric substance, the ratio of monomer 1 is 60～98 weight %, the total ratio of monomer 2 and monomer 3 is 1～39 weight %, and the ratio of monomer 4 is 1～39 weight %.
16. according to Claim 8 or the manufacture method of phosphate-based polymers of 9 records, wherein, in the whole monomers that use in the polymkeric substance, the ratio of monomer 3 is 1～15 weight %.
17. according to the manufacture method of the phosphate-based polymer of claim 10 record, wherein, in the whole monomers that use in the polymkeric substance, the ratio of monomer 3 is 1～15 weight %.
18. according to the manufacture method of the phosphate-based polymer of claim 11 record, wherein, in the whole monomers that use in the polymkeric substance, the ratio of monomer 3 is 1～15 weight %.
19. according to the manufacture method of the phosphate-based polymer of claim 13 record, wherein, in the whole monomers that use in the polymkeric substance, the ratio of monomer 3 is 1～15 weight %.
20. the purposes that is used for dispersant for hydraulic composition of the polymkeric substance that the manufacture method of the polymkeric substance of any record of claim 1～5 or any record by claim 8～19 obtains.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006009155 | 2006-01-17 | ||
| JP009155/2006 | 2006-01-17 | ||
| JP2006133398 | 2006-05-12 | ||
| JP133398/2006 | 2006-05-12 | ||
| PCT/JP2007/050867 WO2007083786A1 (en) | 2006-01-17 | 2007-01-16 | Dispersing agent for hydraulic composition |
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| Publication Number | Publication Date |
|---|---|
| CN101370747A CN101370747A (en) | 2009-02-18 |
| CN101370747B true CN101370747B (en) | 2011-10-05 |
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| CN2007800025011A Active CN101370747B (en) | 2006-01-17 | 2007-01-16 | Dispersant for hydraulic composition |
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| CN (1) | CN101370747B (en) |
| ES (1) | ES2362018T3 (en) |
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| FR2974090B1 (en) | 2011-04-15 | 2013-05-31 | Chryso | COPOLYMERS WITH GEM-BISPHOSPHONE GROUPS |
| EP2824124A1 (en) * | 2013-07-12 | 2015-01-14 | Basf Se | Polymeric dispersing agent |
| JP6629723B2 (en) * | 2014-04-24 | 2020-01-15 | 東邦化学工業株式会社 | Carbon blocker for hydraulic compositions |
| CN106117455B (en) * | 2016-06-22 | 2018-10-16 | 科之杰新材料集团有限公司 | A kind of cross-linking type muting sensitive sense polycarboxylate water-reducer and preparation method thereof |
| CN106046269B (en) * | 2016-06-22 | 2018-09-07 | 科之杰新材料集团有限公司 | A kind of cross-linking type muting sensitive sense ester ether copoly type polycarboxylate water-reducer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1223981A (en) * | 1998-01-21 | 1999-07-28 | 林哲山 | Cement disperser and its preparing method |
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| CN1223981A (en) * | 1998-01-21 | 1999-07-28 | 林哲山 | Cement disperser and its preparing method |
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| Title |
|---|
| JP特开2000-327386A 2000.11.28 |
| JP特开2003-206169A 2003.07.22 |
| JP特开2004-2172A 2004.01.08 |
| JP特开2004-75977A 2004.03.11 |
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| ES2362018T3 (en) | 2011-06-27 |
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