CN101189197A - Powdery cement dispersant - Google Patents

Powdery cement dispersant Download PDF

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CN101189197A
CN101189197A CNA200680019297XA CN200680019297A CN101189197A CN 101189197 A CN101189197 A CN 101189197A CN A200680019297X A CNA200680019297X A CN A200680019297XA CN 200680019297 A CN200680019297 A CN 200680019297A CN 101189197 A CN101189197 A CN 101189197A
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repeating unit
methyl
polycarboxylic acid
cement dispersant
hydrogen atom
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川上宏克
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Nippon Shokubai Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42Ethers, e.g. polyglycol ethers of alcohols or phenols
    • C09K23/44Ether carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04Polymers provided for in subclasses C08C or C08F
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14Polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16Amines or polyamines
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40Surface-active agents, dispersants
    • C04B2103/408Dispersants

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides a polycarboxylic acid type powdery cement dispersant having superior dispersing performance. The present invention provides a powdery cement dispersant which contains a polycarboxylic acid type copolymer having a repeating unit (I) derived from an unsaturated polyalkyleneglycol ether type monomer (a) and a repeating unit (II) derived from an unsaturated carboxylic acid type monomer (b) and having neutralization degree of carboxyl groups contained in the polycarboxylic acid type copolymer is not higher than 50%. The present invention also provides a powdery cement dispersant which comprises a polycarboxylic acid type copolymer comprising a repeating unit (I) derived from an unsaturated polyalkyleneglycol ether type monomer (a) and a repeating unit (II) derived from an unsaturated carboxylic acid type monomer (b), and the unsaturated polyalkyleneglycol ether type monomer (a) comprising an alkenyl group having 4 to 8 carbon atoms.

Description

Powdery cement dispersant
Technical field
The present invention relates to powdery cement dispersant, especially, relate to and be included in the powdery cement dispersant that its pendant moiety has the polycarboxylic acid polymkeric substance of polyalkylene oxide part.
Background technology
Concrete has become in the modern society one of must obligato material, and is widely used for various application, for example buildings, house, bridge and tunnel.Concrete contains cement, water by sclerosis usually and the concrete composition that gathers materials forms.In this concrete composition, mix the various spikes except that these materials, with the various performances of enhancing coagulation local soil type thing, for example flowability, aerating and freeze-thaw resistance.
As one of spike, the known water cement dispersant.Usually have higher weather resistance owing to have the concrete of less water-content, therefore the water yield of preferably mixing in the concrete composition is low as far as possible.Yet the water yield of mixing is very few, can not guarantee the abundant flowability of concrete composition, causes reducing workability.Cement dispersants has the function that minimizing will be mixed the water yield in the concrete composition, helps head it off.
As one of cement dispersants, the known polycarboxylic acid cement dispersants that in polymer repeat unit, contains carboxylic acid or its salt.In addition, also known can passing through with polyalkylene oxide (PAO:-(AO) n-) introduce the flowability that improves grout in the polycarboxylic acid polymkeric substance.Compare with traditional naphthalene class or melamine class cement dispersants, the polycarboxylic acid cement dispersants of introducing polyalkylene oxide the cement dispersibility, under fresh state cement composition flowability, flow keep performance, separating resistance and hardened material intensity manifest more excellent performance.
The polycarboxylic acid cement dispersants of this introducing polyalkylene oxide can be according to being divided into several classes as the monomer of raw material and the bonding scheme of polyalkylene oxide.These classes comprise: for example wherein with (methyl) vinylformic acid or its salt as one of starting material monomer and polyalkylene oxide is bonded to polymkeric substance (the alkenyl PAO ether/acrylic acid structure: of another starting material monomer backbone by ehter bond referring to following formula (1), wherein COOY represents carboxyl or its salt), wherein with toxilic acid, fumaric acid or its salt are bonded to the polymkeric substance (alkenyl PAO ether/toxilic acid structure: referring to following formula (2)) of another starting material monomer backbone as one of starting material monomer and by ehter bond with polyalkylene oxide, and wherein will (methyl) vinylformic acid or its salt be used as one of starting material and polyalkylene oxide be bonded to the polymkeric substance (PAO (methyl) acrylate/(methyl) acrylic acid structure :) of another starting material monomer backbone by ester bond referring to following formula (3).In addition, keep carboxylic acid or become metal-salt, various polymkeric substance can be divided into acids, monovalent metal salt, divalent metal salt, trivalent metal salt etc. according to carboxylic moiety.
Figure S200680019297XD00021
Traditionally, for example, the monovalent metal salt base polymer of open PAO (methyl) acrylate of JP-A-2000-26145/(methyl) acrylic acid structure and PAO (methyl) acrylate/alkenyl PAO ether/(methyl) acrylic acid structure.In addition, for example, the monovalent metal salt base polymer of open PAO (methyl) acrylate of JP-A-2002-167255/(methyl) acrylic acid structure and alkenyl PAO ether/acrylic acid structure.In addition, for example, the divalent metal salt base polymer of open PAO (methyl) acrylate of JP-A-2002-167256/(methyl) acrylic acid structure and alkenyl PAO ether/acrylic acid structure.Further, the divalent metal salt base polymer of the open alkenyl PAO ether of JP-A-9-309756/toxilic acid structure for example.
In order to improve the characteristic of cement dispersants, the technology that polycarboxylic acid polymkeric substance wherein adds another component has been proposed.For example, open wherein with polycarboxylic acid polymkeric substance and PEG blended cement dispersants (referring to for example JP-A-2000-26146).In addition, open wherein by addition polymerization with alkylene oxide mix polycarboxylic acid polymkeric substance and polyalkylene polyamine cement composition (referring to, for example, JP-A-2000-109357).
Summary of the invention
Aforesaid polycarboxylic acid cement dispersants uses with liquid form usually.Yet, consider transportation cost etc., cement dispersants preferably is pulverulence.Also require cement dispersants to have high dispersibility.Yet wherein polyalkylene oxide partly is present in the traditional polycarboxylic acid cement dispersants in the polymkeric substance, even also tend to be wax shape or pulpous state when water removed, and is difficult to pulverize (pulverized).
Therefore, the purpose of this invention is to provide good dispersibility of performance and the method that is easy to pulverize in the polycarboxylic acid cement dispersants.
After the method for head it off is furtherd investigate, the inventor finds: have in the polycarboxylic acid polymkeric substance with ad hoc structure of polyalkylene oxide part at its side chain, be not higher than preset value by the degree of neutralization that is controlled at the carboxyl that contains in this multipolymer, or adopt the unsaturated alkylene glycol ethers monomer that contains alkenyl as the monomer that in multipolymer, produces repeating unit with predetermined carbonatoms, usually the solution that contains the polycarboxylic acid polymkeric substance that is difficult to pulverize can easily be pulverized and do not lost its dispersing property, has finished the present invention based on this understanding.
Particularly, according to an aspect of the present invention, the powdery cement dispersant that contains the polycarboxylic acid multipolymer is provided, this polycarboxylic acid multipolymer has derived from the repeating unit (I) of unsaturated alkylene glycol ethers monomer (a) with derived from the repeating unit (II) of unsaturated carboxylic acid class monomer (b), and the degree of neutralization with the carboxyl that contains in this polycarboxylic acid multipolymer is not higher than 50%.
In addition, according to a further aspect in the invention, the powdery cement dispersant that contains specific copolymer that the good dispersibility of performance is provided and can is easy to pulverize.Particularly, the powdery cement dispersant that contains the polycarboxylic acid multipolymer is provided, this polycarboxylic acid multipolymer has derived from the repeating unit (I) of unsaturated alkylene glycol ethers monomer (a) with derived from the repeating unit (II) of unsaturated carboxylic acid class monomer (b), and this unsaturated alkylene glycol ethers monomer (a) contains the alkenyl with 4 to 8 carbon atoms.
By with reference to and consider the preferred embodiment of example in the following description, will know other purposes of the present invention, feature and advantage.
Description of drawings
Fig. 1 is the photo that is presented at the cement dispersants of producing among the embodiment 2 of the present invention.
Fig. 2 is the photo of the Dian Fentang pulpous state composition that shows that the polycarboxylic acid polymer composition produce by drying obtains in comparative example 1.
Embodiment
As the method that is used to pulverize the polycarboxylic acid cement dispersants, known for example be used for and cement dispersants part or all of hydroxy-acid group is converted into the method for metallic salt form.Yet the result of study by the inventor is clear that: the dispersing property of cement dispersants reduces along with the increase of metal-salt ratio in the polymkeric substance.
Result as the inventor further studies is clear that: the polyalkylene oxide part is introduced in the polycarboxylic acid polymkeric substance, even make that the pulverizing of this polymkeric substance is also easier under sour form state by ehter bond.In addition, also be clear that: under with the part carboxyl neutral situation in the polymkeric substance, even when degree of neutralization is low, also can obtain to have the polycarboxylic acid powdery cement dispersant of good dispersion energy.Its mechanism is unclear, but ester bond has certain effect for the volatilization of moisture according to estimates.Yet this mechanism is only for estimating that technical scope of the present invention should never be limited to this mechanism.
Then, provide detailed description about cement dispersants of the present invention.
One aspect of the invention is the powdery cement dispersant that comprises the polycarboxylic acid multipolymer, this polycarboxylic acid multipolymer has derived from the repeating unit (I) of unsaturated alkylene glycol ethers monomer (a) with derived from the repeating unit (II) of unsaturated carboxylic acid class monomer (b), and the degree of neutralization with the carboxyl that contains in this polycarboxylic acid multipolymer is not higher than 50%.
Contain the polycarboxylic acid multipolymer and can from the solution producing, easily pulverize, and have the high dispersive performance as the cement dispersants of main ingredient.
Hereinafter, will illustrate in this respect by this repeating unit of example (I) and repeating unit (II).For example, the structure of the polycarboxylic acid multipolymer that contains in this powdery cement dispersant in is in this regard represented by following Chemical formula 1.
[Chemical formula 1]
Figure S200680019297XD00051
In this Chemical formula 1, R 1Expression hydrogen atom or methyl.Consider monomeric copolymerization, R 1Preferable methyl.
In this Chemical formula 1, R 2Expression hydrogen atom or have the alkyl of 1 to 30 carbon atom.Described alkyl comprises for example alkyl, alkenyl, aryl and alkyl phenyl.This type of alkyl comprises for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group and cyclohexyl.In addition, " alkenyl " means by general formula C nH 2n-1The monoradical of wherein the either carbon atom of a hydrogen atom from alkene being removed of expression.This alkenyl comprises for example vinyl, allyl group, propenyl and pseudoallyl.In addition, aryl comprises for example phenyl and naphthyl, and alkyl phenyl comprises for example aminomethyl phenyl and ethylphenyl.Consider flowability, R 2Preferred hydrogen atom or methyl.
In this Chemical formula 1, R 3And R 4Each represent independently hydrogen atom, methyl or-COOM 2, condition is with R 3And R 4Be-COOM 2Situation get rid of.In addition, R 5Expression hydrogen atom, methyl or-CH 2COOM 3, condition is to work as R 5For-CH 2COOM 3The time, R 3And R 4Each represent hydrogen atom or methyl independently and do not represent-COOM 2In addition, in this Chemical formula 1, M 1, M 2And M 3Each represent hydrogen atom, atoms metal, ammonium or organic ammonium independently.Work as M 1, M 2Or M 3During for atoms metal, described atoms metal can be any unit price, divalence and tervalent, and particularly, suitable atoms metal comprises the monovalent metal atom, as alkali metal atom such as lithium, sodium and potassium; Divalent metal atom is as alkaline earth metal atom such as calcium and magnesium; With trivalent metal atom such as aluminium and iron.Wherein, from improving the viewpoint of pulverizing easiness, M 1, M 2Or M 3Preferred monovalent metal atom or divalent metal atom.In addition, this ammonium " NH that serves as reasons 3 +" expression functional group.This organic ammonium for example comprises the residue derived from following organic amine, as alkanolamine such as monoethanolamine, diethanolamine and trolamine; Alkylamine such as mono aminoethane, diethylamine and triethylamine; With polyamines such as quadrol and triethylenediamine.
Work as R 3And R 4Each when being hydrogen atom, can (work as R for derived from propylene acid at the repeating unit (II-a) on Chemical formula 1 right side 5Be hydrogen atom) and methacrylic acid (work as R 5Be methyl) part.In addition, work as R 4Be carboxyl and R 3And R 5During for hydrogen atom, the repeating unit (II-a) on the Chemical formula 1 right side can be the part derived from toxilic acid and fumaric acid.In addition, work as R 3And R 4Be hydrogen atom and R 5For-CH 2During the COOH base, the repeating unit (II-a) on this Chemical formula 1 right side can be the part derived from methylene-succinic acid.
In this Chemical formula 1, AO represents to have the oxyalkylene group of 2 to 18 carbon atoms." A " that constitute this type of oxyalkylene group comprises for example ethylidene, propylidene, methyl ethylidene, ethyl ethylidene, styrene, Aden's methyl and 1,2-dimethyl ethylidene.That is, " AO " in Chemical formula 1 is for containing the oxyalkylene group (for example, oxyethylene group) of above-mentioned functional group.Wherein, from the viewpoint of excellent fluidity, A is preferably ethylidene or methyl ethylidene.In addition, inhomogeneous AO structure can randomly be present in by (AO) more than 2 kinds nIn the repeating unit of expression.Yet, consider this polyoxyalkylene chain of easy production and its structure of control, should be by (AO) nThe unitary repeating structure of the preferred identical AO of repeating unit of expression.
In this Chemical formula 1, R aExpression has the alkylidene group of 0 to 2 carbon atom.Here, " alkylidene group with 0 carbon atom " means wherein O (AO) nR 2Direct Bonding does not contain any by R to the carbon atom that constitutes main chain aThe structure of the part of expression.In addition, the R that has 1 carbon atom aMean wherein backbone c atoms and O (AO) nR 2By the structure that methylene radical connects, has the R of 2 carbon atoms aMean wherein backbone c atoms and O (AO) nR 2Structure by ethylidene or methyl methylene radical (methylmethylene group) connection.
In this Chemical formula 1, n means the average addition mole number by the oxyalkylene group of " AO " expression, and is 2 to 300 integer.From good flowability with pulverize the viewpoint of easiness, n is preferred 10 to 200, and more preferably 20 to 150.
Consider the pulverizing easiness, it is preferred 1,000 to 500,000 to have the weight-average molecular weight (being converted into polyoxyethylene glycol) of polycarboxylic acid multipolymer of the repeating unit of being represented by Chemical formula 1, and more preferably 5,000 to 100,000.About this point, be to measure the weight-average molecular weight value, use the method for describing among the embodiment below.
As the monomer of the repeating unit (I-a) that is formed on the Chemical formula 1 left side, comprise the alkylene oxide addition compound of the unsaturated alcohol that obtains in the following manner: 2 to 300 moles of alkylene oxides are added to unsaturated alcohol for example vinyl alcohol, allyl alcohol, methacrylic alcohol, isoprene alcohol (3-methyl-3-butene-1-alcohol) etc.Its two or more can be used in combination.
In addition, the monomer as the repeating unit (I-a) that forms the Chemical formula 1 left side can use commercially available compound, maybe can be by synthesizing the compound of preparation separately.In this is synthetic, can be suitably with reference to the knowledge that has obtained.For example, when alkylene oxide is added to unsaturated alcohol, alkylene oxide such as oxyethane, propylene oxide, butylene oxide ring etc. can be added to unsaturated alcohol such as allyl alcohol, methacrylic alcohol, isoprene alcohol (3-methyl-3-butene-1-alcohol).Temperature condition when carrying out the addition reaction of alkylene oxide does not limit especially, yet, preferred 80 to 155 ℃, more preferably 90 to 150 ℃.
As the monomer of the repeating unit that is formed on this Chemical formula 1 right side (II-a), comprise vinylformic acid, methacrylic acid, toxilic acid etc.Its two or more can be used in combination.
Monomer as the repeating unit (II-a) that forms this Chemical formula 1 right side also can use commercially available compound, maybe can be by synthesizing the compound of preparation separately.
The repeating unit (I-a) in Chemical formula 1 left side is not particularly limited with the content ratio of the repeating unit (II-a) on Chemical formula 1 right side, but the dispersiveness that consideration is wished etc. are suitably determined.This ratio (I-a)/(II-a) is preferably 50-99/50-1 quality %, more preferably 60-95/4-5 quality %, and further preferred 70-95/30-5 quality % is based on repeating unit (I-a) and the 100 quality % of total amount (II-a).
In addition, the oxyalkylene units that contains in repeating unit (I-a) (hereinafter being also referred to as " AO unit (a) ") does not limit especially with the content ratio of carboxylic acid (salt) unit (hereinafter being called " COOH unit (a) ") that contains in repeating unit (II-a).Yet, for making cement dispersants show good balance by the absorptive character of carboxyl with between by the dispersing property of polyoxyalkylene part, AO unit (a) sum: preferred 1: 1 to 50: 1 of the ratio of COOH unit (a) sum, more preferably 4: 1 to 30: 1, further more preferably 7: 1 to 25: 1.The sum of AO unit (a) and COOH unit (a) can pass through 1H-NMR method or alkalimetry are calculated.
Have in the polycarboxylic acid multipolymer of the repeating unit of representing by Chemical formula 1 at this, can also contain the repeating unit except that repeating unit (I-a) and repeating unit (II-a).Monomer as forming these other repeating units can comprise for example having sulfonic unsaturated sulfonic acid such as 2-(methyl) acrylamide-2-methyl propane sulfonic acid, 2-hydroxyl-3-allyloxy propane sulfonic acid, (methyl) vinylformic acid sulfo group ethyl ester, (methyl) vinylformic acid sulfo group propyl ester and styrene sulfonic acid; Its monovalent metal salt, divalent metal salt, ammonium salt or organic ammonium salt; Unsaturated amides is as (methyl) acrylamide and (methyl) propenyl alkylamide; Vinyl ester such as vinyl-acetic ester and propionate; Styrene derivatives such as vinylbenzene and bromstyrol etc.These repeating units are by obtaining to exist through random polymerization, block polymerization, alternating polymerization or similar polymerization.
Yet, for make the good dispersing property of this cement dispersants performance and produce in be easy to pulverize, these two kinds of repeating units of being represented by Chemical formula 1 are preferably the main repeating unit of polycarboxylic acid multipolymer.Particularly, above-mentioned two kinds of necessary repeating units are preferably with 50 to 100%, and more preferably 80 to 100% contain, based on the repeating unit sum in this polycarboxylic acid multipolymer.
About this point, in having the polycarboxylic acid multipolymer of the repeating unit of being represented by Chemical formula 1, repeating unit (I-a), repeating unit (II-a) and other repeating unit can be with block form copolymerization or can random copolymerization or can alternating copolymerization.
The main ingredient polycarboxylic acid multipolymer of powdery cement dispersant of the present invention is even therein not with under the carboxyl neutral acid form state, also can easily pulverize.In the case, the part of the carboxyl that contains in this polycarboxylic acid multipolymer can exist with salt form by neutralization.Preferred univalent ion of counter ion that produces by neutralization and more preferably sodium ion.When these counter ion be divalence (for example, calcium ion), trivalent or more when high price, when this multipolymer must contain the concrete composition of water and cement and cement composition when its adding, exist to be difficult to be dissolved in the shortcoming in the water that constitutes this concrete composition and cement composition and postpone the performance of dispersion effect.In addition, when being used for the aqueous solution after this cement dispersants is transported to the place of working with favourable powder-form in transporting, this multipolymer is difficult to water-soluble, and it causes the reduction of workability.On the contrary, the ratio by neutralization reduction carboxyl causes reducing as the dispersing property of cement dispersants.The ratio of therefore, neutralization part is preferably less.Particularly, this multipolymer has following feature: have the degree of neutralization of determining by following equation and be not higher than 50%, and this degree of neutralization preferably is not higher than 30%, more preferably no higher than 10%.By suppressing degree of neutralization, can obtain to have the cement dispersants of good dispersion energy to low value.
Wherein, consider cement dispersing property and pulverizing easiness, degree of neutralization preferred especially 0%.That is, as the polycarboxylic acid multipolymer, wherein there is not the neutral carboxyl in preferred especially the use, just sour form the sort of completely.
Degree of neutralization (%)=[j/ (j+k)] * 100
Wherein j is illustrated in the sum of the carboxyl that exists with salt form in this polycarboxylic acid multipolymer; K is illustrated in the sum of the carboxyl that exists with non-neutral acid form in this polycarboxylic acid multipolymer.
About this point, can measure this degree of neutralization by pH measurement or alkalimetry.In addition, when comprising the repeating unit that contains carboxyl during as other repeating units, these carboxyls that are included in other repeating unit also count when calculating this degree of neutralization.Therefore, in the carboxyl that comprises in other repeating unit, the ratio of sour form is also preferred higher and ratio salt form is preferably lower.
The method that is used to produce the multipolymer of powdery cement dispersant main ingredient of the present invention does not limit especially, and this multipolymer can be synthetic based on the conventional known method.This multipolymer can be synthetic based on the knowledge of new acquisition.As starting material, can prepare monomer corresponding to repeating unit.
Equally also do not limit especially with the drying mode that the pulverizing multipolymer obtains powdery cement dispersant of the present invention by drying.This drying mode can be selected according to the character of this multipolymer.The drying mode that is used to comprise the solution of this multipolymer comprises for example dry and comminuting method, salting-out process, coagulating sedimentation method, freeze-drying, condense and break and desiccating method, spray-drier method, rotary drum dryer method and conveyor dryer method.Wherein, consider, can preferably use the drying mode (for example, freeze-dried method) of less this multipolymer of heating from the viewpoint that prevents this multipolymer thermal destruction.For example, in this freeze-dried method, the solution that contains this multipolymer uses liquid nitrogen etc., and cooling is freezing rapidly, and this frozen copolymer solution uses the Freeze Drying Equipment drying under reduced pressure subsequently.By this method, can obtain to have for example fine particle of about 40nm to 500 μ of particle diameter m.Equally, in the spray-drier method, use spray-drier with this copolymer solution atomizing, and in air, mix to carry out drying with warm air.By this method, can obtain to have the fine particle that particle diameter for example is not more than 100 μ m.In addition, in rotary drum dryer method or conveyor dryer method, use rotary drum dryer or conveyor dryer that this copolymer solution drying and forming-film so that film thickness are no more than 100 μ m, then this film is pulverized and classification.For example, by these methods, can obtain to have the fine particle that median size for example is no more than 300 μ m.About this point, pulverize the fine grain particle diameter that obtains by drying and can further use selectivity pulverizing/hierarchical approaches to adjust, to obtain to have the powdery cement dispersant of wishing particle diameter.
Preferred 1 to the 500 μ m of the median size of the main ingredient polycarboxylic acid multipolymer of powdery cement dispersant of the present invention, more preferably 10 to 100 μ m.Median size has this powdery cement dispersant less than 1 μ m and is tending towards adherent danger, and median size surpasses 500 μ m and can cause reducing for the solubleness of water and reduce dispersibility for cement.
Another aspect of the present invention is the powdery cement dispersant that contains the polycarboxylic acid multipolymer, this polycarboxylic acid multipolymer has derived from the repeating unit (I) of unsaturated alkylene glycol ethers monomer (a) with derived from the repeating unit (II) of unsaturated carboxylic acid class monomer (b), and this unsaturated alkylene glycol ethers monomer (a) contains the alkenyl with 4 to 8 carbon atoms.In this respect, consider monomeric polymerizability and raw-material operability, the carbonatoms of the alkenyl that comprises in the monomer (a) that forms repeating unit (I) is preferred 4 to 6, and more preferably 4 to 5.
Hereinafter, will illustrate in this respect by this repeating unit of example (I) and repeating unit (II).For example, the structure of the polycarboxylic acid multipolymer that comprises in this powdery cement dispersant in is in this regard represented by following Chemical formula 2.
[Chemical formula 2]
Figure S200680019297XD00121
This Chemical formula 2 has the structure that is similar to Chemical formula 1.
In this Chemical formula 2, R 1, R 2, AO, n, R 3, R 4, R 5And M 1Identical with the definition in the Chemical formula 1.Therefore, it is described in detail in this omission.Certainly, the concrete pattern at the repeating unit on Chemical formula 2 right side is identical with Chemical formula 1.
In this Chemical formula 2, R bExpression has the alkylidene group of 1 to 2 carbon atom.R bConcrete pattern and R in this Chemical formula 1 aIdentical, so it is described in detail in this omission.
Form the monomer of the repeating unit (I-b) in Chemical formula 2 left side, can be by 2 to 300 moles alkylene oxide being added to unsaturated alcohol such as methallyl alcohol or isoprene alcohol (3-methyl-3-butene-1-alcohol) etc. obtain.
In addition, the monomer as the repeating unit (I-b) that is formed on the Chemical formula 2 left side can use commercially available compound, maybe can be by synthesizing the preparation compound separately, and this is identical with Chemical formula 1.
In this respect of the present invention, the degree of neutralization of the carboxyl that comprises in the polycarboxylic acid multipolymer does not limit especially.About this point, the degree of neutralization in the present invention in this respect preferably is no more than 80%, more preferably no more than 50%, and further more preferably no more than 30%.
In the powdery cement dispersant in the present invention in this respect, the concrete pattern of other except that this degree of neutralization equally with aspect the present invention is above-mentioned in powdery cement dispersant identical.Therefore, it is described in detail in this omission.
The repeating unit (I-b) in Chemical formula 2 left side with at the content of the repeating unit (II-b) on Chemical formula 2 right side than not limiting especially, but consider that desirable dispersibility etc. suitably determines.The preferred 50-99/50-1 quality % of this ratio (I-b)/(II-b), more preferably 60-95/4-5 quality %, and further preferred 70-95/30-5 quality % is based on repeating unit (I-b) and the 100 quality % of total amount (II-b).
In addition, the content of the oxyalkylene units that contains in this repeating unit (I-b) (below be also referred to as " AO unit (b) ") and carboxylic acid (salt) unit that contains in this repeating unit (II-b) (below be also referred to as " COOH unit (b) ") is than not limiting especially.Yet, for making this cement dispersants show good balance by the absorptive character of carboxyl with between by the dispersing property of polyoxyalkylene part, AO unit (b) sum: preferred 1: 1 to 50: 1 of the ratio of COOH unit (b) sum, more preferably 4: 1 to 30: 1, further more preferably 7: 1 to 25: 1.The sum of AO unit (b) and COOH unit (b) can pass through 1H-NMR method or alkalimetry are calculated.
Use the purpose of the powdery cement dispersant of the invention described above to be, by it being added the dispersibility that cement composition such as grout, mortar and concrete improve cement composition.This dispersion agent can also be used for super high strength concrete.In this cement composition, can mix common used material such as cement, water, sand and coarse aggregate.In this cement composition, fine particle such as flyash, blast-furnace slag, silicon ash and Wingdale can be added.About this point, super high strength concrete means the usually so concrete of name, that is, even when the ratio with water/cement compared with conventional concrete reduces, its hardened material is compared with conventional concrete and also shown and be equal to or more high-intensity concrete.For example, super high strength concrete is such concrete: out of question and its hardened material has compressive strength and preferably is not less than 60N/mm its workability for common use 2, more preferably be not less than 80N/mm 2, further more preferably be not less than 100N/mm 2, also further more preferably be not less than 120N/mm 2, especially preferably be not less than 160N/mm 2, most preferably be not less than 200N/mm 2Even, when the ratio of water/cement preferably is no more than 25 quality %,,, especially preferably be no more than 14 quality % further more preferably no more than 18 quality % more preferably no more than 20 quality %, be most preferably not exceeding 12 quality %.
As cement, portland cement such as common, high early strong, super early strong, fast hard, middle heat of hard water and white cement; Mixing portland cement is suitable as alundum cement, pulverized fuel ash cement, slag cement and silicon-dioxide cement.The amount of the cement that mixes and the concrete unit of the every 1m3 water yield are as follows.For example, be to produce high-durability and strong concrete, the preferred unit water yield is 100 to 185kg/m 3And the ratio of water/cement=10 are to 70%.More preferably, the unit water yield is 120 to 175kg/m 3And the ratio of water/cement=20 are to 65%.
When using powdery cement dispersant of the present invention, preferred adjusting will be added to the amount of the powdery cement dispersant of the present invention in the cement composition, so that the quantitative change of powdery cement dispersant of the present invention becomes 0.01 to 1.0 quality %, with respect to the cement composition of 100 quality %.When the add-on of powdery cement dispersant during less than 0.01 quality %, its performance may be not enough, and when this add-on surpasses 1.0 quality %, may reduce its economical efficiency, not corresponding to the add-on raising dispersibility that increases.In addition, the add-on of powdery cement dispersant is 0.05 to 0.5 quality % more preferably, and further more preferably 0.1 to 0.3 quality % is with respect to the cement composition of 100 quality %.About this point, the unit of quality % means the value that is converted into the solid composition.
Powdery cement dispersant of the present invention is added in the cement composition, and the combination of powdery cement dispersant of the present invention with its two or more compositions can be added in the cement composition.In this cement composition, can mix other additive.For example, except that powdery cement dispersant of the present invention, in this cement composition, can add other cement dispersants, air, cement wetting agent, swelling agent, water-resisting agent, retardant, quick-setting additive, water soluble polymer material, thickening material, flocculation agent, drying shrinkage-reducing agent, intensity reinforcing agent, hardening accelerator, defoamer etc.
The suitable embodiment of the combination of powdery cement dispersant of the present invention and other additive comprises that following (1) is to (7).
(1) comprises the composition of following material:<1〉powdery cement dispersant of the present invention and<2〉the oxyalkylene defoamer as necessary component.As the oxyalkylene defoamer, can use polyoxyalkylene, polyoxyalkylene alkyl, polyoxyalkylene acetylene ether, polyoxyalkylene alkylamine etc.Wherein, the polyoxyalkylene alkylamine is especially suitable.<2〉the oxyalkylene defoamer mix preferred 0.01 to the 20 quality % of mass ratio, with respect to 100 quality %<1〉powdery cement dispersant.
(2) comprise of the combination of following 3 kinds of components:<1〉powdery cement dispersant of the present invention,<2〉oxyalkylene defoamer and<3〉AE agent as necessary component.As the oxyalkylene defoamer, can use polyoxyalkylene, polyoxyalkylene alkyl, polyoxyalkylene acetylene ether, polyoxyalkylene alkylamine etc.Wherein, the polyoxyalkylene alkylamine is especially suitable.As the AE agent, resin acid soaps (resinate soap), alkyl sulfonic ester and alkyl phosphate are especially suitable.<2〉the oxyalkylene defoamer mix preferred 0.01 to the 20 quality % of mass ratio, with respect to 100 quality %<1〉powdery cement dispersant.<3〉the AE agent mix preferred 0.001 to the 2 quality % of mass ratio, for the cement composition of 100 quality %.
(3) comprise of the combination of following 3 kinds of components:<1〉powdery cement dispersant of the present invention,<2 as necessary component〉by polyalkylene glycol list (methyl) acrylic ester monomer, (methyl) acrylic monomer and the multipolymer and<3 that can form with the monomer (being disclosed in JP-B-59-18338, JP-A-7-223852, JP-A-9-241056 etc.) of these monomer copolymerizations〉the oxyalkylene defoamer, this polyalkylene glycol list (methyl) acrylic ester monomer has the polyoxyalkylene chain that has the alkylene oxide of 2 to 18 carbon atoms with average addition mole number 2 to 300 additions.<1〉powdery cement dispersant and<2〉multipolymer mix preferred 5/95 to 95/5 (powdery cement dispersant/multipolymer) of mass ratio, more preferably 10/90 to 90/10.<3〉the oxyalkylene defoamer mixes than preferred 0.01 to 20 quality %, with respect to<1〉powdery cement dispersant and<2〉the total amount 100 quality % of multipolymer.
(4) comprise of the combination of following 2 kinds of components:<1〉powdery cement dispersant of the present invention and<2〉retardant as necessary component.As retardant, can use oxycarboxylic acid such as glyconic acid (its salt) and citric acid (its salt); Carbohydrate such as glucose; Sugar alcohol such as Sorbitol Powder; With phosphonic acids as amino-three-(methylene phosphonic acid).<1〉powdery cement dispersant and<2〉retardant mix preferred 50/50 to 99.9/0.1 (powdery cement dispersant/retardant) of mass ratio, more preferably 70/30 to 99/1.
(5) comprise of the combination of following 2 kinds of components:<1〉powdery cement dispersant of the present invention and<2〉promotor as necessary component.As promotor, can use soluble calcium salt such as calcium chloride, calcium nitrite and nitrocalcite; Muriate such as iron(ic) chloride and magnesium chloride; Thiosulphate; Formic acid; With formate such as calcium formiate.<1〉powdery cement dispersant and<2〉promotor mix preferred 10/90 to 99.9/0.1 (powdery cement dispersant/promotor) of mass ratio, more preferably 20/80 to 99/1.
(6) comprise of the combination of following 2 kinds of components:<1〉powdery cement dispersant of the present invention and<2〉the material separation depressant as necessary component.As the material separation depressant, can use hydrophobic substituent that various thickening materials such as nonionic cellulose ether and having be made up of the hydrocarbon chain with 4 to 30 carbon atoms and the compound of the polyoxyalkylene chain of the alkylene oxide with 2 to 18 carbon atoms as part-structure be arranged with average addition mole number 2 to 300 additions.<1〉powdery cement dispersant and<2〉the material separation depressant mix preferred 10/90 to 99.99/0.01 (powdery cement dispersant/material separation depressant) of mass ratio, more preferably 50/50 to 99.9/0.1.Cement composition with this combination is suitable for high-flowing concrete, self-compacting concrete and self-leveling material.
(7) comprise of the combination of following 2 kinds of components as necessary component:<1〉powdery cement dispersant of the present invention and<have sulfonic sulfonic acid class dispersion agent in 2〉molecule.As sulfonic acid class dispersion agent, can use sulfonated lignin, naphthene sulfonic acid formalin condenses, melamine sulfonic acid formalin condenses, poly styrene sulfonate, thionamic acid class dispersion agent such as amino-aryl sulfonic acid-P-F condenses etc.<1〉powdery cement dispersant and<2〉sulfonic acid class dispersion agent mix preferred 5/95 to 95/5 (powdery cement dispersant/sulfonic acid class dispersion agent) of mass ratio, more preferably 10/90 to 90/10.
Be used to prepare the qualification especially of method of concrete composition, can use and the similar method of method that is used for conventional cement composition.For example, comprise powdery cement dispersant of the present invention and cement mixing and further mix other in case of necessity and mix material, add entry and blended method subsequently; Prepare the solution that contains cement dispersants and this solution added and be mixed to the method that contains in the composition that cement and other mix material etc. by prior dissolving cement dispersants of the present invention.
Embodiment
Below, illustrate in greater detail the present invention by using embodiment, but technical scope of the present invention is not limited only to the following examples.About this point, in embodiment described below, the measurement of the weight-average molecular weight of polycarboxylic acid multipolymer is carried out under measuring condition described below by GPC.
Unit type: Waters LCM1;
Detector: Waters 410 differential refraction detectors;
Analysis software: Waters Millennium Ver.2.18;
Elutriant: by the 115.6g sodium acetate trihydrate is dissolved in 10,999g water and 6 in the mixture of 001g acetonitrile, and is adjusted to pH6 with 30% aqueous sodium hydroxide solution and prepares elutriant;
Eluent flow rate: 0.8ml/min;
Column temperature: 35 ℃;
Post: TSKgel Guardcolumn SWXL+G4000SWXL+G3000SWXL+G2000SWXL, produced by TosohCorp; With
Reference material: polyoxyethylene glycol, weight-average molecular weight (Mw): 272,500,219,300,85,000,46,000,24,000,12,600,4,250,7,100 and 1,470.
Embodiment 1-1
The glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is equipped with in preparation.76.91g water and 149.28g in this reactor, pack into as the repeating unit (I-a) in the formation Chemical formula 1 or the monomeric unsaturated alkylene glycol ether of the repeating unit (I-b) in the Chemical formula 2, this unsaturated alkylene glycol ether obtains by average 50 moles oxyethane (EO) being added to 3-methyl-3-butene-1-alcohol (3M3B1O), under stirring this aqueous solution with reactor in nitrogen replacement after, under nitrogen atmosphere, this solution is heated to 60 ℃.After internal temperature is stabilized in 60 ℃, add the aqueous hydrogen peroxide solution of forming by 0.23g hydrogen peroxide and 11.71g water.Then, in 3 hours and 3.5 hours, drip 20.17g is dissolved in 40.74g water as the monomeric vinylformic acid (AA) that forms repeating unit (II-a) in the Chemical formula 1 or the repeating unit (II-b) in the Chemical formula 2 and 0.3g L-xitix and 0.79g 3-thiohydracrylic acid the aqueous solution respectively.Subsequently, the temperature by keeping this polymeric reaction solution continued this polyreaction 1 hour at 60 ℃ again.After this polymerization is finished, this reaction product of dilute with water, consequently will consolidate constituent concentration is adjusted to 40 quality %, to obtain the aqueous solution (1-1).The weight-average molecular weight (Mw) of this polycarboxylic acid multipolymer (1-1) in obtained aqueous solution (1-1) is 37,000, and the pH of this aqueous solution (1-1) is 3.4.Polymer content is 90% by gpc measurement.About this point, for method of calculation, this polymer content is measured by such method, in the method, by GPC figure obtain corresponding to the area of this polymeric constituent divided by corresponding to the area of this polymeric constituent with corresponding to the summation of the area of the unsaturated alkylene glycol ether component of remnants.In addition, calculate the ratio of AO unit in this polycarboxylic acid multipolymer (1-1) ((a) or (b)) sum and COOH unit ((a) or (b)) sum.The result proves that this ratio is 10.5: 1.Simultaneously, calculate this ratio according to following equation.
AO unit sum=l * m * n=149.28/2286 * 90 * 50=293.86
COOH unit sum=p * q=20.17/72 * 100=28.01
Wherein, l represents to form the mole number of repeating unit (I-a) or monomeric unsaturated alkylene glycol ether (I-b), m represents the polymerization ratio (%) of unsaturated alkylene glycol ether, and n is illustrated in the average addition mole number of the oxyethane in this unsaturated alkylene glycol ether.In addition, p represents to form repeating unit (II-a) or monomeric acrylic acid mole number (II-b), and q represents polymerizing acrylic acid ratio (%).
Use the aqueous solution (1-1) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Embodiment 1-2
By be adjusted in pH to 5.0 ± 0.5 of the aqueous solution (1-1) that obtains among the embodiment 1-1 with sodium hydroxide, obtain the aqueous solution (1-2).The degree of neutralization of this polycarboxylic acid multipolymer (1-2) in this obtained aqueous solution (1-2) is 30%.
Use the aqueous solution (1-2) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Embodiment 1-3
By be adjusted in pH to 6.5 ± 0.5 of the aqueous solution (1-1) that obtains among the embodiment 1-1 with sodium hydroxide, obtain the aqueous solution (1-3).The degree of neutralization of this polycarboxylic acid multipolymer (1-3) in this obtained aqueous solution (1-3) is 80%.
Use the aqueous solution (1-3) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Embodiment 1-4
By be adjusted in pH to 6.5 ± 0.5 of the aqueous solution (1-1) that obtains among the embodiment 1-1 with calcium hydroxide, obtain the aqueous solution (1-4).The degree of neutralization of this polycarboxylic acid multipolymer (1-4) in this obtained aqueous solution (1-4) is 80%.
Use the aqueous solution (1-4) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Embodiment 2
The glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is equipped with in preparation.The 64.62g water of in this reactor, packing into, with 120.00g as forming the repeating unit (I-a) in the Chemical formula 1 or the monomeric unsaturated alkylene glycol ether of the repeating unit (I-b) in the Chemical formula 2, this unsaturated alkylene glycol ether obtains by average 20 moles oxyethane (EO) being added to 3-methyl-3-butene-1-alcohol (3M3B1O), under stirring this aqueous solution with reactor in nitrogen replacement after, under nitrogen atmosphere, this solution is heated to 58 ℃.After internal temperature is stabilized in 58 ℃, add the aqueous hydrogen peroxide solution of forming by 0.60g hydrogen peroxide and 29.32g water.Then, respectively in 3 hours and 3.5 hours, drip the aqueous solution that is dissolved in 51.55g water by 22.74g as the monomeric vinylformic acid (AA) that forms repeating unit (II-a) in the Chemical formula 1 or the repeating unit (II-b) in the Chemical formula 2 and the aqueous solution that 9.74g water is formed and 0.78g L-xitix and 0.65g 3-thiohydracrylic acid.Subsequently, the temperature by keeping this polymeric reaction solution continued this polyreaction 1 hour at 58 ℃ again.After this polymerization was finished, the solid constituent concentration of this reaction soln was 49 quality %.With this reaction soln called after aqueous solution (2).The weight-average molecular weight of this polycarboxylic acid multipolymer (2) in obtained aqueous solution (2) is 31,000, and the pH of this aqueous solution (2) is 3.2.
Use the aqueous solution (2) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Embodiment 3
The glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is equipped with in preparation.The 150.00g water of in this reactor, packing into, with 100.00g as forming the repeating unit (I-a) in the Chemical formula 1 or the monomeric unsaturated alkylene glycol ether of the repeating unit (I-b) in the Chemical formula 2, this unsaturated alkylene glycol ether obtains by average 150 moles oxyethane (EO) being added to methallyl alcohol (MTA), under stirring this aqueous solution with reactor in nitrogen replacement after, under nitrogen atmosphere, this solution is heated to 60 ℃.After internal temperature is stabilized in 60 ℃, add the aqueous hydrogen peroxide solution of forming by 0.07g hydrogen peroxide and 3.37g water.Then, respectively in 3 hours and 3.5 hours, drip the aqueous solution that is dissolved in 12.26g water by 6.21g as the monomeric vinylformic acid (AA) that forms repeating unit (II-a) in the Chemical formula 1 or the repeating unit (II-b) in the Chemical formula 2 and the aqueous solution that 4.14g water is formed and 0.09g L-xitix and 0.16g 3-thiohydracrylic acid.Subsequently, the temperature by keeping this polymeric reaction solution continued this polyreaction 1 hour at 60 ℃ again.After this polymerization was finished, the solid constituent concentration of this reaction soln was 39 quality %.With this reaction soln called after aqueous solution (3).The weight-average molecular weight of this polycarboxylic acid multipolymer (3) in obtained aqueous solution (3) is 69,000, and the pH of this aqueous solution (3) is 3.9.
Use the aqueous solution (3) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Embodiment 4
The glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is equipped with in preparation.The 144.34g water of in this reactor, packing into, 217.46g as the monomeric unsaturated alkylene glycol ether that forms repeating unit (I-a) in the Chemical formula 1 or the repeating unit (I-b) in the Chemical formula 2 and 22.53g as the monomeric toxilic acid (MA) that forms repeating unit (II-b) in repeating unit (II-a) in the Chemical formula 1 or the Chemical formula 2, this unsaturated alkylene glycol ether obtains by average 50 moles oxyethane (EO) being added to 3-methyl-3-butene-1-alcohol (3M3B1O), under stirring this aqueous solution with reactor in nitrogen replacement after, under nitrogen atmosphere, this solution is heated to 63 ℃.After internal temperature is stabilized in 63 ℃, add the aqueous hydrogen peroxide solution of forming by 0.20g hydrogen peroxide and 0.46g water.Then, in 1 hour, dropping is dissolved in the aqueous solution of forming in the 14.75g water by the 0.26gL-xitix.Subsequently, the temperature by keeping this polymeric reaction solution continued this polyreaction 1 hour at 63 ℃ again.After this polymerization was finished, the solid constituent concentration of this reaction soln was 60 quality %.With this reaction soln called after aqueous solution (4).The weight-average molecular weight of this polycarboxylic acid multipolymer (4) in obtained aqueous solution (4) is 29,000, and the pH of this aqueous solution (4) is 2.7.
Use the aqueous solution (4) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Embodiment 5
The glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is equipped with in preparation.76.91g water and 149.28g in this reactor, pack into as the monomeric unsaturated alkylene glycol ether that forms the repeating unit (I-a) in the Chemical formula 1, this unsaturated alkylene glycol ether obtains by average 50 moles oxyethane (EO) being added to vinyl carbinol (ALA), under stirring this aqueous solution with reactor in nitrogen replacement after, under nitrogen atmosphere, this solution is heated to 60 ℃.After internal temperature is stabilized in 60 ℃, add the aqueous hydrogen peroxide solution of forming by 0.23g hydrogen peroxide and 11.71g water.Then, respectively in 3 hours and 3.5 hours, drip 20.17g is dissolved in 40.74g water as the monomeric vinylformic acid (AA) that forms the repeating unit (II-a) in the Chemical formula 1 and 0.3g L-xitix and 0.79g 3-thiohydracrylic acid the aqueous solution.Subsequently, the temperature by keeping this polymeric reaction solution continued this polyreaction 1 hour at 60 ℃ again.After this polymerization is finished, this reaction product of dilute with water consequently will be consolidated constituent concentration and be adjusted to 40 quality % to obtain the aqueous solution (5).The weight-average molecular weight (Mw) of this polycarboxylic acid multipolymer (5) in obtained aqueous solution (5) is 16,000, and the pH of this aqueous solution (5) is 3.4.Polymer content is 53% by gpc measurement.In addition, according to embodiment 1-1 in identical method, calculate the ratio of AO unit (a) sum and COOH unit (a) sum in this polycarboxylic acid multipolymer (5).The result proves that this ratio is 6.3: 1.Use the aqueous solution (5) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Comparative example 1
The glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is equipped with in preparation.The 100.01g water of in this reactor, packing into, in stirring under water with reactor with nitrogen replacement after, under nitrogen atmosphere, this solution is heated to 80 ℃.After internal temperature is stabilized in 80 ℃, in 4 hours and 5 hours, drip respectively by mixing 112.59g methoxy poly (ethylene glycol) monomethacrylates (MPEGMA; 25), the 169.99g monomer solution that obtains of 22.41g methacrylic acid (MAA), 33.40g water and 1.24g3-thiohydracrylic acid and the 30g aqueous solution of dissolving 1.55g ammonium persulphate the average addition mole number of oxyethane:.Subsequently, the temperature by keeping this polymeric reaction solution continued this polyreaction 1 hour at 80 ℃ again.After this polymerization was finished, the solid constituent concentration of reaction soln was 47 quality %.With this reaction soln called after aqueous solution (A).The weight-average molecular weight (Mw) of this polycarboxylic acid multipolymer (A) in obtained aqueous solution (A) is 23,000, and the pH of this aqueous solution (A) is 2.2.
Use the aqueous solution (A) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Comparative example 2
The glass reactor of thermometer, agitator, dropping funnel, nitrogen ingress pipe and reflux exchanger is equipped with in preparation.The 99.25g water of in this reactor, packing into, in stirring under water with reactor with nitrogen replacement after, under nitrogen atmosphere, this solution is heated to 70 ℃.After internal temperature is stabilized in 70 ℃, in 4 hours and 5 hours, drip respectively by mixing 106.68g methoxy poly (ethylene glycol) monomethacrylates (MPEGMA; 10), the 170.48g monomer solution that obtains of 28.32g methacrylic acid (MAA), 33.31g water and 1.73g3-thiohydracrylic acid and the 30g aqueous solution of dissolving 1.55g ammonium persulphate the average addition mole number of oxyethane:.Subsequently, the temperature by keeping this polymeric reaction solution continued this polyreaction 1 hour at 70 ℃ again.After this polymerization is finished, the dilute with water reaction product, the solid constituent concentration of reaction soln is adjusted to 40 quality %, to obtain the aqueous solution (B).The weight-average molecular weight (Mw) of this polycarboxylic acid multipolymer (B) in this obtained aqueous solution (B) is 14,000, and the pH of this aqueous solution (B) is 3.9.
Use the aqueous solution (B) that obtains as mentioned above, attempt as described later pulverizing, whether can pulverize to estimate this solution.
Pulverize test
The aqueous solution that use obtains in each embodiment and comparative example (1-1 to 1-4,2 to 5, A and B) is pulverized test by the following method.
Each aqueous solution is provided to the petri dish of the glass with 13cm diameter, so that dry back solid content is 20g.50 ℃ and 50 holders (about 6.7 * 10 3Pa) under the environment this solution was placed 24 hours, anhydrated to remove.After the drying, solid was placed in moisture eliminator one day, in mortar, products therefrom is pulverized.With the powder pulverized sieve, to obtain the having powdery cement dispersant that specified particle diameter distributes by 16 sieve meshes.
Estimate whether each above-mentioned solution can both be pulverized by aforesaid method.Evaluation result is shown in the following table 1.Estimate according to following standard:
Zero: obtain to have mobile powdery cement dispersant;
*: solid becomes pulpous state or adhesive film, can not pulverize.
[table 1]
Monomer 1 (repeating unit (I-a) or (I-b)) Monomer 2 (repeating unit (II-a) or (II-b)) Degree of neutralization (salt) EO bonding state Mw Pulverize and estimate
Embodiment 1-1 3M3B1O+50EO AA Not neutralization Ether 37000
Embodiment 1-2 3M3B1O+50EO AA 30%(Na) Ether 37000
Embodiment 1-3 3M3B1O+50EO AA 80%(Na) Ether 37000
Embodiment 1-4 3M3B1O+50EO AA 80%(Ca) Ether 37000
Embodiment 2 3M3B1O+20EO AA Not neutralization Ether 31000
Embodiment 3 MTA+150EO AA Not neutralization Ether 69000
Embodiment 4 3M3B1O+50EO MA Not neutralization Ether 29000
Embodiment 5 ALA+50EO AA Not neutralization Ether 16000
Comparative example 1 MPEGMA(EO:25) MAA Not neutralization Ether 23000 ×
Comparative example 2 MPEGMA(EO:10) MAA Not neutralization Ether 14000 ×
As shown in table 1, this polycarboxylic acid multipolymer with polyalkylene oxide part as the cement dispersants main ingredient in, show: the degree of neutralization by the carboxyl that will contain in this multipolymer suppresses to low-level, the aqueous solution of this multipolymer can be easily contained, and powdery cement dispersant can be obtained by drying and crushing.
About this point, for reference, by will in embodiment 2, being shown among Fig. 1 by the photo of the dry powder that obtains of obtained aqueous solution (2).In addition, the photo of the starch paste composition that obtains of the aqueous solution (B) by gained in the dry comparative example 1 is shown among Fig. 2.
The mortar test
For studying the dispersibility of powdery cement dispersant of the present invention, the mortar test adds in the mortar by the powdery cement dispersant that will obtain by the aqueous solution (1-1) to (1-4) and the aqueous solution (5) of acquisition among pulverizing embodiment 1-1 to 1-4 and the embodiment 5 respectively to be carried out.
The following description of cement composition.
TAIHEIYO normal portland cement: 900g
Standard sand by the JISR5201 definition: 1,350g
Water: 270g
By using mixing machine and the blending means that is similar to according to the blending means of 10.4.3 item among the JIS R 5201, measure mortar according to the flow test of JIS R 5201 and flow.With regard to this point, before the mixing, powdery cement dispersant is mixed in the cement composition.Measuring result is shown in the following table 2.In table 2, the add-on of this powdery cement dispersant is represented based on the % of the cement that changes into solid composition.
[table 2]
Powdery cement dispersant Degree of neutralization (salt) Add-on (wt%/C) Mortar flow (mm) Volume of air (vol%)
(1-1) Not neutralization 0.12 226 6.5
(1-2) 30%(Na) 0.12 224 6.2
(1-3) 80%(Na) 0.12 216 6.3
(1-4) 80%(Ca) 0.12 205 6.2
(5) Not neutralization 0.12 190 5.8
As shown in table 2, with have the powdery cement dispersant (1-3) of degree of neutralization and compare up to 80%, the powdery cement dispersant that derives from embodiment 1-1 (1-1) that wherein multipolymer is not neutralized and have degree of neutralization and be low to moderate 30% the powdery cement dispersant that derives from embodiment 1-2 (1-2) provides higher yield point value.That is, find: compare with the dispersing property of the cement dispersants (1-3) of embodiment 1-3, the powdery cement dispersant (1-2) of the powdery cement dispersant of embodiment 1-1 (1-1) and embodiment 1-2 provides higher cement dispersing property.
In addition, find that compare with the cement dispersing property of the cement dispersants (1-4) of embodiment 1-4, the cement dispersants of embodiment 1-3 (1-3) provides higher cement dispersing property.Think that this is because sodium ion has the ability of the generation multipolymer high resolution higher than calcium ion.In addition, find: compare with the cement dispersing property of the cement dispersants (5) of embodiment 5, the cement dispersants of embodiment 1-1 (1-1) provides higher cement dispersing property.Think that this is that cement dispersants (5) has the multipolymer content of lower level because compare with cement dispersants (1-1), this causes the reduction of active component content.
The Japanese patent application No.2005-162049 that the application submitted to based on June 1st, 2005, its whole disclosures are hereby incorporated by.

Claims (8)

1. powdery cement dispersant, it comprises the polycarboxylic acid multipolymer, this polycarboxylic acid multipolymer comprises derived from the repeating unit (I) of unsaturated alkylene glycol ethers monomer (a) with derived from the repeating unit (II) of unsaturated carboxylic acid class monomer (b), and the degree of neutralization with the carboxyl that contains in this polycarboxylic acid multipolymer is not higher than 50%.
2. powdery cement dispersant according to claim 1, wherein this polycarboxylic acid multipolymer comprises the repeating unit of being represented by following Chemical formula 1:
[Chemical formula 1]
Figure S200680019297XC00011
R wherein 1Expression hydrogen atom or methyl, R 2Expression hydrogen atom or have the alkyl of 1 to 30 carbon atom, each AO represents to have the oxyalkylene group of 2 to 18 carbon atoms, R independently aExpression has the alkylidene group of 0 to 2 carbon atom, and n represents the average addition mole number of oxyalkylene group and is 2 to 300, R 3And R 4Each represent independently hydrogen atom, methyl or-COOM 2(condition is with R 3And R 4Be-COOM 2Situation get rid of), R 5Expression hydrogen atom, methyl or-CH 2COOM 3(condition is to work as R 5For-CH 2COOM 3The time, R 3And R 4Each represent hydrogen atom or methyl independently), M 1, M 2And M 3Each represent hydrogen atom, atoms metal, ammonium or organic ammonium independently.
3. powdery cement dispersant according to claim 1 and 2, wherein this R 1Be methyl.
4. according to each described powdery cement dispersant of claim 1 to 3, wherein this R 3, R 4And R 5Be hydrogen atom.
5. according to each described powdery cement dispersant of claim 1 to 4, wherein this A is ethylidene or methyl ethylidene.
6. according to each described powdery cement dispersant of claim 1 to 5, wherein this degree of neutralization is 0%.
7. powdery cement dispersant, it comprises the polycarboxylic acid multipolymer, this polycarboxylic acid multipolymer comprises derived from the repeating unit (I) of unsaturated alkylene glycol ethers monomer (a) with derived from the repeating unit (II) of unsaturated carboxylic acid class monomer (b), and this unsaturated alkylene glycol ethers monomer (a) comprises the alkenyl with 4 to 8 carbon atoms.
8. powdery cement dispersant according to claim 7, wherein this polycarboxylic acid multipolymer comprises the repeating unit of being represented by following Chemical formula 2:
[Chemical formula 2]
Figure S200680019297XC00021
R wherein 1Expression hydrogen atom or methyl, R 2Expression hydrogen atom or have the alkyl of 1 to 30 carbon atom, R bExpression has the alkylidene group of 1 to 2 carbon atom, and each AO represents to have the oxyalkylene group of 2 to 18 carbon atoms independently, and n represents the average addition mole number of oxyalkylene group and is 2 to 300, R 3And R 4Each represent independently hydrogen atom, methyl or-COOM 2(condition is with R 3And R 4Be-COOM 2Situation get rid of), R 5Expression hydrogen atom, methyl or-CH 2COOM 3(condition is to work as R 5For-CH 2COOM 3The time, R 3And R 4Each represent hydrogen atom or methyl independently), M 1, M 2And M 3Each represent hydrogen atom, atoms metal, ammonium or organic ammonium independently.
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