CN101081920A - Dispersion comprising silicon dioxide and polycarboxylate ether - Google Patents
Dispersion comprising silicon dioxide and polycarboxylate ether Download PDFInfo
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- CN101081920A CN101081920A CNA2007100077906A CN200710007790A CN101081920A CN 101081920 A CN101081920 A CN 101081920A CN A2007100077906 A CNA2007100077906 A CN A2007100077906A CN 200710007790 A CN200710007790 A CN 200710007790A CN 101081920 A CN101081920 A CN 101081920A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- Curing Cements, Concrete, And Artificial Stone (AREA)
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Abstract
A dispersion which is free of binders and which contains silicon dioxide and at least one water-soluble polycarboxylate ether, where - the silicon dioxide is a pyrogenic silicon dioxide which is present in the form of aggregated primary particles having a BET surface area of 50 to 250 m2/g, and - the aggregates in the dispersion have a mean diameter of less than 1 [mu]m, - based on the total amount of the dispersion, - the water-soluble polycarboxylate ether is a copolymer based on at least one oxyalkylene glycol compound and at least one unsaturated monocarboxylic acid derivative or dicarboxylic acid derivative, - the weight ratio of polycarboxylate ether/silicon dioxide is 0.01 to 100.
Description
Technical field
The present invention relates to based on the dispersion of silicon-dioxide and polycarboxylate ether with and as the purposes of concrete additive.
Background technology
For example by knowing for a long time among the US3135617 that settled acceleration can realize by soft silica in small, broken bits.Yet this does not obtain certainly, because therefore the applicability of fresh concrete is subjected to very big restriction.
In WO02/070429, a kind of matrix material that comprises inorganic aggregate, ultra-fine particles, the tackiness agent that contains cement and concrete super plasticizing agent is disclosed.
This matrix material allows to produce the highly concrete of liquefaction, does not occur oozing out phenomenon therein.Used ultra-fine particles mainly is " silicon ash " particle, and it obtains with the silicon metal." silicon ash " particle is that 150nm or bigger spherical individual particles exist as diameter usually.In cement or concrete composition, they have shown strong filler effect, but because its low specific surface area, they do not have strong reactivity here.The particle of other spendable this order of magnitude is kaolin, flying dust, volcanic ash, lime carbonate, aluminum oxide, barium sulfate and titanium dioxide.Described particle has the little shortcoming of specific surface area, and this nucleation rate that has caused intensity to form phase hangs down and also therefore causes low early strength.Early strength is interpreted as the concrete strength behind cement hydration＜48h in the context of the present invention.
The ratio of described ultra-fine particles is 1-30 weight % based on the total amount of matrix material, is about 10-25 weight % based on the summation of cement and ultra-fine particles in an embodiment perhaps.Therefore the requirement of ultra-fine particles is very high.
In US6752866, a kind of method of improving early strength is disclosed, wherein in cement, added the aqueous dispersion that contains mineral filler and special dispersing agent.As mineral filler, can use lime carbonate, barium carbonate, Wingdale, rhombspar, talcum, silicon-dioxide, titanium dioxide, diatomite, ferric oxide, magnesium oxide, lime, kaolin, clay, mica, gypsum, flying dust, slag, calcium sulfate, zeolite, basalt, barium sulfate or aluminium hydroxide.The preferred lime carbonate that uses.The median size of disclosed used mineral filler is that about 2 μ m are to about 10 μ m.Special dispersing agent is necessary for invention disclosed in US6752866.It contains the multipolymer that the radical copolymerization by alkoxyl group polyalkylene glycol urea alkane and negatively charged ion or non-ionic monomer obtains.Do not provide the actual detail of the requirement of mineral filler, dispersion agent and cement.The content of being inferred mineral filler by embodiment is 10 weight % (silicon-dioxide based on silicon-dioxide, test number 12) or 30 weight % (silicon-dioxide, test number 17), and the content of dispersion agent be 0.5 weight % (test number 17) or 0.75 weight % (test number 12).These dispersions only demonstrate low stability to sedimentation.
WO01/90024 discloses a kind of concrete composition that contains aggregate, hydraulic binder, silicon sol and polycarboxylate.The preferred 300-900m of BET surface-area of this silicon sol
2/ g.Silicon sol is that diameter is 3-50nm and stable individual particles in dispersion only.In WO01/90024, do not have open about of the influence of described silicon sol to early strength.Yet those skilled in the art are known to be reached under the remarkable thickness of silica gel that increases of early strength, and applicability significantly descends, and therefore needs a large amount of super plasticizing agents.This is silicon sol rapid dissolved fact in alkaline cement or concrete composition according to hypothesis.Therefore this silicon sol only can be used as on not half and is used to form the nucleus that intensity forms calcium silicate hydrate.
WO98/12149 discloses a kind of aggregate, hydraulic binder and BET surface-area of containing less than 200m
2The silicon sol of/g, wherein size-grade distribution should make silicon sol the relative standard deviation of numeric distribution greater than 30%, be about 45-70% in an embodiment.The present invention seeks to increase early strength and can not reduce final strength.Wherein super plasticizing agent can be added in the concrete composition.Yet use the super plasticizing agent that is disclosed in WO98/12149 to cause silicon sol to have the rapid decline of following process period.In WO98/12149, illustrate based on tackiness agent and need be preferably the particle of 1-8% and particularly advantageously be that 2% particle is to realize the increase of early strength.Those skilled in the art are known, and remarkable decline of applicability also therefore need a large amount of super plasticizing agents under the situation of this high thickness of silica gel.Therefore, Wagner and Hauck are in Wiss.Z.Hochsch.Archit.Bauwesen.-Weimar40 (1990), point out in the 183rd page when using the thickness of silica gel of＞1% cement, the content of super plasticizing agent must be significantly greater than 1% the concrete of cement content to obtain being easy to process.A large amount of super plasticizing agents causes expensive for the user and also can often cause detrimental action, and for example stronger tendency oozes out and lower final strength.
In EP-A-1607378, for containing the cement system, a kind of additive based on fumed metal oxides has been described, it contains at least a sorbent material.Described fumed metal oxides can exist with the form of aqueous dispersion.In addition, can use super plasticizing agent based on polycarboxylate.Yet EP-A-1607378 both not about the details of polycarboxylate type, did not have the scope of the necessary polycarboxylate amount that adds yet, not about adding the step mode of polycarboxylate yet.In addition, in the time of should pointing out that the additive of describing is the dispersion form in EP-A-1607378, sedimentation had low stability.
In Wiss.Z.Hochsch.Archit.Bauwesen.-Weimar40 (1990), in the 183rd page, Wagner and Hauck point out, if when using oxide compound to increase early strength, then the needs of the interpolation of various compositions time ordered pair early strength and super plasticizing agent have remarkably influenced in concrete production.In this research, oxide compound and super plasticizing agent are separately added.Result in conjunction with flowing agent and oxide compound in concrete additive has reduced possible different interpolations time ordinal number, and has therefore also reduced fault rate.Other advantage of this bonded in a kind of concrete additive is only to need an adding set, and this is the representative cost advantage for the user.
Prior art shows that exploitation is had high early strength and has good applicability simultaneously and needn't use the interest of concrete composition of a large amount of softening agent very active.Prior art shows that also super plasticizing agent and the particle in present available cement or the concrete composition is responsive system.For example, the adding order of used material and concentration have crucial influence to concrete applicability and early strength.
Summary of the invention
Therefore, the objective of the invention is to obtain a kind ofly the shortcoming of prior art to be reduced to minimum concrete additive.Particularly, this concrete additive should make concrete early strength significantly increase and have good applicability simultaneously.
The present invention relates to a kind of dispersion that contains silicon-dioxide and at least a water soluble polycarboxylic acid ester ether, wherein
-described silicon-dioxide is pyrolytic silicon dioxide, and it is, and gathering primary granule form exists and the BET surface-area is 50-250m
2/ g, wherein
Aggregate in the-dispersion have less than the mean diameter of 1 μ m and
The ratio of-silicon-dioxide is 5-50 weight % based on the dispersion total amount,
-described water soluble polycarboxylic acid ester ether is based on the multipolymer of at least a oxyalkylene diol compound and at least a unsaturated monocarboxylic derivative or dicarboxylic acid derivatives,
The weight ratio of-polycarboxylate ether/silicon-dioxide is 0.01-100.
In the present invention, term silicon-dioxide and silica dioxide granule refer to same substance.
Dispersion of the present invention is preferably aqueous dispersion, and promptly the main component of liquid phase is a water.Described liquid phase also contains water soluble polycarboxylic acid ester ether.
Dispersion of the present invention does not contain tackiness agent.Therefore here tackiness agent is interpreted as inorganic substance such as cement or organic substance, and it is machinable in the plasticity attitude, and is cured in specified time and is bonded to each other with other material.
Pyrolysis is interpreted as the silica dioxide granule that obtains by flame oxidation and/or flame hydrolysis.The operable initial substance that is used for pyrolysis method is organic and inorganic substance.For example silicon tetrachloride is especially suitable.Suitable organic starting compound for example can be Si (OR)
4, R=CH wherein
3Or CH
2CH
3The silica dioxide granule that obtains thus be to the full extent atresia and have free hydroxyl group from the teeth outwards.In meaning of the present invention, described fumed silica particle to small part exists with the form of assembling primary granule.Usually, fumed silica particle is aggregated forms to the full extent.
Dispersion of the present invention also can contain the pyrolysis mixed oxide, and it contains silicon-dioxide as first component and contain Lithium Oxide 98min, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, aluminum oxide or zirconium dioxide as second component.The mixture that can have equally, pyrolytic silicon dioxide and above-mentioned mixed oxide.
Preferred pyrolysis mixed oxide is by aerosol the mixed oxide component to be introduced wherein those.For example they are the mixed oxide of silicon-potassium or the mixed oxide of silicon-lithium, they for example can according to DE-A-19650500 or application number be 05024753.5 and the date of application be that the still undocumented european patent application on November 11st, 2005 prepares.In addition, can contain can be according to the silicon-aluminium-mixed oxide of EP-A-995718 preparation for dispersion of the present invention.Described mixed oxide is only being that the primary granule of minuent is assembled and noticeable.
Advantageously pyrolytic silicon dioxide is optional from the AEROSIL available from Degussa
90, AEROSIL
130, AEROSIL
200, AEROSIL
TT600, AEROSIL
MOX80, AEROSIL
MOX170; CAB-O-SIL available from Cabot Corp.
LM-150, CAB-O-SIL
LM-150D, CAB-O-SIL
M-5, CAB-O-SIL
M-5P, CAB-O-SIL
M-5DP, CAB-O-SIL
M-7D, CAB-O-SIL
PTG, CAB-O-SIL
HP-60; HDK available from Wacker
S13, HDK
V15, HDK
V15P, HDK
N20, HDK
N20P; REOLOSIL available from Tokuyama
QS-10, REOLOSIL
QS-20, REOLOSIL
QS-30, REOLOSIL
QS-40, REOLOSIL
DM-10.
Silicon-dioxide of the present invention also can surface modification form exist.Therefore, the surface can for example be crossed by halo organosilane, organoalkoxysilane, silazane, siloxanes, polysiloxane surface modification.Preferred used silanizing agent is Trimethoxyoctylsilane [(CH
3O)
3-Si-C
8H
17], octamethylcyclotetrasiloxane or hexamethyldisilazane.Because the stability of dispersion of the present invention is usually lower under the situation than non-modified silicon-dioxide under through the situation of the silicon-dioxide of surface modification, the preferred latter.
In addition, dispersion of the present invention can contain pyrolytic silicon dioxide as unique solid.When described dispersion conduct was used for the masterbatch of multiple application, this was especially useful.
The BET surface area limitation that will be present in the silicon-dioxide in the dispersion of the present invention is value 50-250m
2/ g.Preferred silicon-dioxide has 70-170m
2The BET surface-area of/g.
In addition, among the preferred 50-500nm of mean diameter of aggregate and the preferred especially 70-300nm in the dispersion of the present invention.Less than the value of 50nm based on pyrolysis produce silicon-dioxide industrial only can obtain difficultly and in application without any better advantage.
In addition, advantageously the relative standard deviation of the numeric distribution of silica aggregate diameter is less than 30%, normally 15-25%.This relative standard deviation is measuring of size-grade distribution.Be used for when of the present invention advantageously narrow as far as possible distribution, promptly alap standard deviation.Can more specifically influence the development of concrete strength by the narrow distribution of aggregate diameter: the aggregate diameter can influence the time point of the hydration acceleration that causes by reactive silicic acid.
Fig. 1 is presented at that two kinds of BET surface-area are 90m in the dispersion of the present invention
2/ g and 200m
2The diameter Distribution of the silica aggregate of/g.The relative standard deviation that the aggregate diameters that records distributes is 23% or 25%.Can especially preferably use these dispersions.
The ratio of silicon-dioxide is 5-50 weight % based on the total amount of dispersion in dispersion of the present invention.Dispersion of the present invention with dioxide-containing silica of 10-30 weight % demonstrates better more stable also therefore for preferred than the dispersion of higher interpolation usually.Because high water-content, the dispersion that contains less than the silicon-dioxide of 5 weight % is not economical.
The weight ratio of polycarboxylate ether/silicon-dioxide is 0.01-100 in the dispersion.Preferred this ratio can be 0.05-5.
The pH of dispersion of the present invention can change in very wide scope.Usually pH can be 2-12, wherein because the consistency of component, and the alkali pH of 8-12, especially 9-11.5 alkali pH can be in cement system preferably.Can for example use ammonia, ammonium hydroxide, Tetramethylammonium hydroxide, organic primary, second month in a season or tertiary amine, sodium hydroxide solution or potassium hydroxide solution as alkali.As acid, can for example use phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid or carboxylic acid.
In addition, aluminium salt can be added in the dispersion of the present invention.Suitable aluminium salt can be aluminum chloride, general formula Al (OH)
xThe aluminium chlorohydroxide of Cl, wherein x=2-8, aluminum chlorate, Tai-Ace S 150, aluminum nitrate, general formula Al (OH)
xNO
3The hydroxyl aluminum nitrate, the mixture of x=2-8, aluminum acetate, alum such as aluminum potassium sulfate or aluminium ammonium sulfate, al formate, Aluctyl, aluminum oxide, acetate aluminium hydroxide, aluminum isopropylate, aluminium hydroxide, pure aluminium silicate and above-claimed cpd wherein.The purposes of these aluminum compounds in the preparation silica dispersion has been described among the DE-A-10238463.
In addition can be advantageously the surfactant of non-ionic type, cationic, anionic or amphoteric type be added in dispersion and/or the predispersion.
Dispersion of the present invention can contain building stone be a), b), c), be preferably a), b), c) and multipolymer d).Here building stone ratio a) is 25-95mol%, building stone b) ratio be 1-48.9mol%, building stone c) ratio be 0-5mol% and building stone d) ratio be 0-47.9mol%.
Particularly, building stone ratio a) is 51-95mol% and building stone c) ratio be 0.1-5mol%.
Described first building stone is monocarboxylic acid-or dicarboxylic acid derivatives of general formula I a, Ib or Ic a).
In monocarboxylic acid derivative I a, R
1Be hydrogen or aliphatic hydrocarbyl with 1-20 C atom, preferable methyl.X among structure I a and the Ib is-OM
aAnd/or-O-(C
mH
2mO)
n-R
2Or-NH-(C
mH
2mO)
n-R
2, wherein M, a, m, n and R
2Have following meaning:
M is hydrogen, monovalence or divalent metal, ammonium, organic amino group, and depends on that M is monovalence or divalent cation and a=1/2 or 1.As organic amino group, preferred use be derived from primary, secondary, uncle C
1-20Alkylamine, C
1-20Alkanolamine, C
5-8Cycloalkyl amine and C
8-14The replacement ammonium of arylamine.The example of corresponding amine is methylamine, dimethylamine, Trimethylamine 99, thanomin, diethanolamine, trolamine, methyldiethanolamine, cyclo-hexylamine, dicyclohexylamine, aniline, the pentanoic that is protonated (ammonium) form.
R
2Be hydrogen, have 1-20 C atom aliphatic hydrocarbyl, have 5-8 C atom the cyclic aliphatic alkyl, have an aryl of 6-14 C atom, described aryl also may optionally be replacement, m can=2-4 and n=0-200.Aliphatic hydrocrbon can be linearity or branching and saturated or undersaturated in this case.Preferred cycloalkyl is cyclopentyl or cyclohexyl, and preferred aryl groups is especially can be by the phenyl or naphthyl of hydroxyl, carboxyl or sulfonic group replacement.
Replace or except the dicarboxylic acid derivatives of formula Ib, building stone a) (monocarboxylic acid-or dicarboxylic acid derivatives) also can exist corresponding to the annular form of formula Ic, wherein Y can=O (acid anhydrides) or have and as above specify meaning R
2NR
2(imide).
The second building stone b) corresponding to formula II and be derived from the oxyalkylene diols alkenyl ether,
Wherein m, n and R
2Have and as above specify meaning.R
3Be hydrogen or the aliphatic hydrocarbyl with 1-5 C atom, it can be linearity or branching or undersaturated equally.P can suppose it is the value of 0-3.
Formula II also comprises the compound that is shown among the formula IIA:
Wherein,
R
3Be hydrogen or aliphatic hydrocarbyl with 1-5 C atom,
P is 0-3,
R
2Be hydrogen or aliphatic hydrocarbyl, have the cyclic aliphatic alkyl of 5-8 C atom, an optional aryl that replaces with 6-14 C atom with 1-20 C atom,
N ' is the value of 0-190.
According to embodiment preferred, m=2 and/or 3 in formula Ia, Ib and II is the polyalkylene oxide groups that is derived from polyethylene oxide and/or poly(propylene oxide) thereby make this group.In a further preferred embodiment, the p among the formula II is 0 or 1, and promptly they are vinyl and/or alkyl poly-alkoxylation thing (alkylpolyalkoxylates).
The 3rd building stone c) corresponding to formula III a or IIIb:
In formula III a, depend on whether relate to acrylic acid derivative or methacrylic acid derivative, R
4Can=H or CH
3In this case S can be-H ,-COOM
aOr-COOR
5, wherein a and M have above-mentioned meaning, and R
5Can be the aliphatic hydrocarbyl with 3-20 C atom, cyclic aliphatic alkyl or aryl with 6-14 C atom with 5-8 C atom.This aliphatic hydrocarbyl can be linearity or branching and saturated or undersaturated equally.Preferred cyclic aliphatic alkyl is that cyclopentyl or cyclohexyl and preferred aryl groups are phenyl or naphthyls.If T=-COOR
5The time, S=COOM then
aOr-COOR
5At T and S=-COOR
5Situation under, corresponding building stone is derived from dicarboxylic ester.
Except that these ester structure unit, building stone c) also can have other hydrophobic structure composition.They comprise poly(propylene oxide) or poly(propylene oxide)-polyethylene oxide derivant, wherein
Here suppose that x is that value and the y of 1-150 is 0-15.Described in this case poly(propylene oxide) (polyethylene oxide) derivative can be via group U
1Be connected in building stone c corresponding to formula III a) ethyl on, U wherein
1Can=-CO-NH-,-O-or-CH
2-O-.They are corresponding acid amides, vinyl ether or allyl ethers corresponding to formula III a building stone.R
6Can be R in this case
2(R
2Meaning see on) or be:
U wherein
2Can=-NH-CO-,-O-or-OCH
2-and S have above-mentioned meaning.These compounds are poly(propylene oxide) (polyethylene oxide) derivative corresponding to the difunctionality alkenyl compound of formula III a.
As other hydrophobic structure composition, can contain the polydimethylsiloxane base corresponding to the compound of formula III a, its in formula III a corresponding to T=-W-R
7
W is in this case:
(polydimethylsiloxane base hereinafter referred to as), R
7Can=R
2And r can suppose it is the value of 2-100 in this case.
This polydimethylsiloxane base not only can be directly but also can be bonded on the ethylidene among the formula III a via following group,
-CO-[NH-(CH
2)
3]
s-W-R
7Or-CO-O (CH
2)
z-W-R
7
R wherein
7Preferably=R
2And s can=1 or 2, and z=0-4.In addition, R
7Also can be:
Here relate to the corresponding difunctionality vinyl compound corresponding to formula III a, it is via the amide group of correspondence or ester group is connected to each other and wherein only have an ethylidene to carry out copolymerization.
T=(CH among this situation and the formula III a
2)
z-V-(CH
2)
z-CH=CH-R
2Compounds seemingly, z=0-4 wherein, V or polydimethylsiloxane base W or-O-CO-C
6H
4-CO-O-base, and R
2Has as above meaning.These compound derivings are in the dialkylene phenyl dicarboxylic ester or the dialkylene polydimethylsiloxanederivative derivative of correspondence.
In the context of the present invention, also not only the ethylidene of one but also two difunctionality vinyl compound carry out copolymerization.This corresponds essentially to the building stone of formula III b:
R wherein
2, V and z have above-mentioned meaning.
The 4th building stone d) be derived from the unsaturated dicarboxylic acid derivatives of general formula I Va and/or IVb, wherein a, M, X and Y have above-mentioned meaning.
Preferred this multipolymer contains the formula Ia of 55-75mol% and/or the building stone of Ib, the building stone of the formula II of 19.5-39.5mol%, the formula III a of 0.5-2mol% and/or the formula IVa of the building stone of IIIb and 5-20mol and/or the building stone of IVb.
According to embodiment preferred, multipolymer of the present invention additionally also contains based on the summation of building stone a-d and is 50mol% at the most, especially at the most 20mol% especially based on following monomeric structure: based on vinyl-or (methyl) acrylic acid derivative such as vinylbenzene, vinyl toluene, vinyl-acetic ester, propionate, ethene, propylene, iso-butylene, (methyl) vinylformic acid hydroxyalkyl acrylate, acrylamide, Methacrylamide, the N-vinyl pyrrolidone, allyl sulphonic acid, methallylsulfonic acid, vinyl sulfonic acid, vinyl phosphonate, AMPS, methyl methacrylate, methyl acrylate, butyl acrylate, the monomer of vinylformic acid allyl group polyhexamethylene.
To repeated structural unit number in the multipolymer without limits.Yet, confirmed that it is particularly advantageous that molecular-weight average is adjusted to 1000-100000g/mol.
Can prepare described multipolymer in many ways.Here the unsaturated monocarboxylic that necessary is makes 51-95mol%-or dicarboxylic acid derivatives, the oxyalkylene alkene ether of 1-48.9mol%, ethene polyalkylene glycol, polysiloxane or the ester cpds of 0.1-5mol% and the dicarboxylic acid derivatives of 0-55mol% carry out polymerization under the help of radical initiator.
The unsaturated list of the used formula that forms Ia, Ib or the building stone of Ic-or dicarboxylic acid derivatives be preferably: vinylformic acid, methacrylic acid, methylene-succinic acid, itaconic anhydride, clothing health imide and methylene-succinic acid monoamide.
Replace vinylformic acid, methacrylic acid, methylene-succinic acid and methylene-succinic acid monoamide, also can use its monovalence or divalent metal salt, preferably use sodium, potassium, calcium or ammonium salt.
It is general formula HO-(C that used acrylate, methacrylic ester or itaconic ester are in particular its alkoxide component
mH
2mO)
n-R
2The derivative of polyalkylene glycol, R wherein
2=H, aliphatic hydrocarbyl, cyclic aliphatic alkyl, the optional aryl that replaces, and m=2-4 and n=0-200 with 6-14 C atom with 5-8 C atom with 1-20 C atom.
On the aryl preferred substituted be-OH ,-COO-or-SO
3Base.
Described unsaturated monocarboxylic derivative only can be used as monoesters and exists, and under the situation of dicarboxylic acid, also can be the methylene-succinic acid diester deriv.
The mixture that the derivative of formula Ia, Ib and Ic also can be used as esterification acid and free acid exists, and the preferred 55-75mol% of consumption.
According to the present invention, second component that is used to prepare multipolymer is the oxyalkylene diols alkenyl ether, the preferred 19.5-39.5mol% of its consumption.In preferred oxidative olefinic diols alkenyl ether corresponding to formula V,
CH
2＝CR
3-(CH
2)
p-O-(C
mH
2mO)
n-R
2 V
R
3=H or have the aliphatic hydrocarbyl and the p=0-3 of 1-5 C atom.R
2, m and n have above-mentioned meaning.Here it is particularly advantageous having confirmed to use polyoxyethylene glycol mono vinyl ether (p=0 and m=2), the value of the preferred 1-50 of n.
Be used to introduce building stone c) ethene polyalkylene glycol, polysiloxane or the ester cpds of the preferred 0.5-2mol% of the 3rd component.Used preferred ethene polyalkylene glycol compounds is the derivative corresponding to formula VI,
Wherein S can preferred-H or COOMa, and U
1=-CO-NH-,-O-or-CH
2O-, promptly they are acid amides, vinyl ether or allyl etherss of corresponding polypropylene glycol or polypropylene glycol-polyethyleneglycol derivative.The x value is 0-150 and V=0-15.R
6Perhaps R
1Perhaps following structure:
U wherein
2=-NH-CO-,-O-and-OCH
2-and S=-COOM
a, and preferred-H.
If R
6=R
2And R
2During preferred H, then relate to polypropylene glycol (polyoxyethylene glycol) monoamide or corresponding vinylformic acid (S=H, R
4=H), methacrylic acid (S=H, R
4=CH
3) or toxilic acid (S=COOM
a, R
4=H) the ether of derivative.This monomeric example is toxilic acid N-(methyl polypropylene glycol) monoamide, toxilic acid N-(methoxyl group polypropylene glycol-polyoxyethylene glycol) monoamide, polypropylene glycol vinyl ether and polypropylene glycol allyl ethers.
If R
6≠ R
2, then relate to the difunctional vinyl compound, its polypropylene glycol (polyoxyethylene glycol) derivative via amide group or ether (O-or-OCH
2-) keyed jointing each other.This examples for compounds is that the polypropylene glycol span comes amido acid, polypropylene glycol diacrylamine, polypropylene glycol DMAA, polypropylene glycol divinyl ether, polypropylene glycol diallyl ether.
Use corresponding to the derivative of formula VII as preferred ethene polysiloxane compound,
R wherein
4=-H and CH
3,
And r=2-100 and preferred R
7=R
1This monomeric example is the mono-vinyl polydimethylsiloxane.
As other ethene polysiloxane compound, suitable derivative is corresponding to those of formula VIII,
Wherein s can=1 or 2, R
4Have above-mentioned meaning with W, and R
7Perhaps can=R
2Perhaps otherwise be following structure,
The preferred hydrogen of S wherein.
This has vinyl functional (R
7=R
2) monomeric example be the amino maleinamic acid of polydimethylsiloxane propyl group maleinamic acid or polydimethylsiloxane dipropylene.If R
7≠ R
2, then they are divinyl compounds, for example polydimethylsiloxane-two (propyl group maleinamic acid) or polydimethylsiloxane-two (the amino maleinamic acid of dipropylene).
As other ethene polysiloxane compound, the preferred derivative that suitable is corresponding to formula IX:
Wherein z can be 0-4 and R
4Or W has above-mentioned meaning.R
7Perhaps R
2Perhaps otherwise be following structure,
The preferred hydrogen of S wherein.This list vinyl compound (R
7=R
1) example be polydimethylsiloxane-(1-propyl group-3 acrylic acid ester) or polydimethylsiloxane-(1-propyl group-3-methacrylic ester).
If R
7≠ R
2, then they are divinyl compounds, for example polydimethylsiloxane-two (1-propyl group-3 acrylic acid ester) or polydimethylsiloxane-two (1-propyl group-3-methacrylic ester).
In the context of the invention, preferred use derivative corresponding to formula X as the vinyl acetate compound,
S=COOM wherein
aOr-COOR
5And R
5Can be the aliphatic hydrocarbyl with 3-20 C atom, cyclic aliphatic alkyl and aryl with 6-14 C atom with 5-8 C atom.A and M have above-mentioned meaning.The example of this ester cpds is n-butyl maleate or di n butyl fumarate or positive butyl ester of toxilic acid list or the positive butyl ester of fumaric acid list.
In addition, also can use compound corresponding to formula XI,
Wherein z can be 0-4 and R
2Has known meaning.V can be W (being the polydimethylsiloxane base) in this case, and it is corresponding to dialkylene polydimethylsiloxane compound such as divinyl polydimethylsiloxane.Perhaps V also can be-O-CO-C
6H
4-CO-O-.These compounds are the derivative of dialkylene phthalic acid.The representative instance of this phthalic acid derivatives is a diallyl phthalate.
The molecular weight of compound formation building stone c) can change in very wide scope, and preferred 150-10000.
Can be used for preparing the unsaturated dicarboxylic acid derivatives (XII) of the preferred 5-20mol% of the 4th component of multipolymer:
M
aOOC-CH＝CH-COX XII
Wherein a, M and X have above-mentioned meaning.
If X=OM
a, then described unsaturated dicarboxylic acid derivatives is derived from monovalence or divalent metal salt such as sodium, potassium, calcium or the ammonium salt of toxilic acid, fumaric acid, these dicarboxylic acid, perhaps with the salt of organic amino group.In addition, the used monomer of formation unit Ia is the polyalkylene glycol mono ester of the above-mentioned acid of general formula X III:
M
aOOC-CH＝CH-COO-(C
mH
2mO)
n-R
2
Wherein a, m, n and R
2Above-mentioned meaning is arranged.
The 4th component also can be derived from unsaturated dicarboxylic acid acid anhydride and the imide (5-20mol%) of general formula X IV,
Wherein Y has above-mentioned meaning.
According to the present invention, embodiment preferred can additionally be used based on building stone summation a)-d) and be 50mol% at the most as mentioned above, preferred other monomer of 20mol% at the most.
Dispersion of the present invention can also contain its basis and be the multipolymer of oxyalkylene group diols alkenyl ether, and described multipolymer contain building stone a), b) and c).Here building stone content a) is 10-90mol%, building stone b) content be 1-89mol%, building stone c) content be 0-5mol% and building stone d) content be 0.1-10mol%.
First building stone is a unsaturated dicarboxylic acid derivatives corresponding to formula IVa and IVb a).
In dicarboxylic acid derivatives corresponding to formula Id, M=hydrogen, monovalence or divalent metal, ammonium ion, organic amino group, and a=1, a=1/2 when perhaps being divalent cation as if M.Itself and one also comprise M then
aThe group of (wherein a=1/2) forms bridged bond via M together, and it is only as the M of a=1/2 in theory
aExist.
As monovalence or divalent metal, preferably use sodium, potassium, calcium or magnesium ion.Used organic amino group is preferably and is derived from primary, the second month in a season or uncle C
1-C
20Alkylamine, C
1-C
20Alkanolamine, C
5-C
8Cycloalkyl amine and C
6-C
14The replacement ammonium of arylamine.The example of corresponding amine is methylamine, dimethylamine, Trimethylamine 99, thanomin, diethanolamine, trolamine, cyclo-hexylamine, dicyclohexylamine, aniline, the pentanoic that is protonated (ammonium) form.In addition, X also is-OM
aOr-O-(C
mH
2mO)
n-R
1, R wherein
1=H, have 1-20 C atom aliphatic hydrocarbyl, have 5-8 C atom the cyclic aliphatic alkyl, have the aryl of 6-14 C atom, described aryl also can be chosen wantonly and replace, m can=2-4 and n=0-200.Described in this case aliphatic hydrocarbyl can be linearity or branching and saturated or undersaturated.
Preferred cycloalkyl is cyclopentyl or cyclohexyl, and preferred aryl groups is a phenyl or naphthyl, and it especially can be replaced by hydroxyl, carboxyl or sulfonic group.Perhaps X can also be-NHR
2And/or-NR
2 2, it replaces or dibasic monoamide, wherein R corresponding to the single of corresponding unsaturated dicarboxylic acid
2Can with R
1Identical or can be-CO-NH
2
Replacement is corresponding to the dicarboxylic acid derivatives of formula IVa, and building stone a) (dicarboxylic acid derivatives) also can exist corresponding to the annular form of formula IVb, wherein Y can=O (=Ic acid anhydrides) or NR
2(imide) and R
2Has above specified meaning.
In second building stone corresponding to formula II,
It is derived from oxyalkylene diols alkenyl ether, wherein R
3Be hydrogen or aliphatic hydrocarbyl (it can be linearity or branching or undersaturated equally) with 1-5 C atom.P can be assumed to the value of 0-3, and R
2, m and n have above-mentioned meaning.According to embodiment preferred, p=0 and m=2 or 3 in formula II, thus be the building stone that is derived from polyethylene oxide or poly(propylene oxide) vinyl ether.
Formula II also comprises the compound that is shown among the formula IIA,
Wherein,
R
3Be hydrogen or aliphatic hydrocarbyl with 1-5 C atom,
P is 0-3,
R
2Be hydrogen, have the aliphatic hydrocarbyl of 1-20 C atom, have the cyclic aliphatic alkyl of 5-8 C atom, the optional aryl that replaces with 6-14 C atom,
N ' is the value of 0-190.
The 3rd building stone c) corresponding to formula III a or IIIb.
In formula III a, depend on whether relate to acrylic or methacrylic acid derivative, R
4Can=H or CH
3In this case S can be-H ,-COOM
aOr-COOR
5, wherein a and M have above-mentioned meaning, and R
5Can be the aliphatic hydrocarbyl with 3-20 C atom, cyclic aliphatic alkyl or aryl with 6-14 C atom with 5-8 C atom.Described aliphatic hydrocarbyl can be linearity or branching and saturated or undersaturated equally.Preferred cyclic aliphatic alkyl is cyclopentyl or cyclohexyl, and preferred aryl groups is a phenyl or naphthyl.If T=-COOR
5, S=-COOM then
aOr-COOR
5If T and S=-COOR
5, then Dui Ying building stone is derived from dicarboxylic ester.
Except that these ester structure unit, building stone c) also can have other hydrophobic structure composition.They comprise poly(propylene oxide) or poly(propylene oxide)-polyethylene oxide derivant, wherein
To be assumed to value and the y of 1-150 be 0-15 to x in this case.This poly(propylene oxide) (polyethylene oxide) derivative can be via group U in this case
1Be connected in building stone c corresponding to formula III a) ethyl on, U wherein
1Can=-CO-NH-,-O-or-CH
2-O-.They are corresponding acid amides, vinyl ether or the allyl ethers corresponding to formula III a building stone in this case.R
6Can be R in this case
1(R
1Meaning see on) or be:
U wherein
2Can=-NH-CO-,-O-or-OCH
2-and S have above-mentioned meaning.These compounds are poly(propylene oxide) (polyethylene oxide) derivative corresponding to the difunctionality alkenyl compound of formula III a.
As other hydrophobic structure composition, can contain the polydimethylsiloxane group corresponding to the compound of formula III a, its in formula III a corresponding to T=-W-R
7
W is in this case:
(polydimethylsiloxane base hereinafter referred to as), R
7Can=R
1And r can be assumed to the value of 2-100 in this case.
Particularly, the ratio of the building stone of formula III a or IIIb is 0.1-10mol%.
This polydimethylsiloxane base W not only can be directly but also can be bonded on the ethylidene among the formula III a via following group,
-CO-[NH-(CH
2)
3]
s-W-R
7Or-CO-O (CH
2)
z-W-R
7,
R wherein
7Preferably=R
1And s can=1 or 2, and z=0-4.
In addition, R
7Can also be:
Here relate to the corresponding difunctionality vinyl compound corresponding to formula III a, it is via the amide group of correspondence or ester group is connected to each other and wherein only have a vinyl to carry out copolymerization.
This situation also with formula III a in T=-(CH
2)
z-V-(CH
2)
z-CH=CH-R
1Compounds seemingly, z=0-4 wherein, V or polydimethylsiloxane base W or-O-CO-C
6H
4-CO-O-base, and R
1Has as above meaning.These compound derivings are in the dialkylene phenyl dicarboxylic ester or the dialkylene polydimethylsiloxanederivative derivative of correspondence.
In the context of the present invention, also not only the vinyl of one but also two difunctionality vinyl compound carry out copolymerization.This corresponds essentially to the building stone of formula III b:
R wherein
1, V and z have above-mentioned meaning.
Preferred these multipolymers are made up of the building stone of the formula II of the building stone of the formula IVa of 40-55mol% and/or IVb, 40-55mol% and the formula III a of 1-5mol% or the building stone of IIIb.According to preferred embodiment, this multipolymer also additionally contain based on building stone a), b) and c) summation be 50mol% at the most, the monomer whose of 20mol% is the building stone of vinyl, acrylic or methacrylic acid derivative especially at the most.
This monomer ethylene radical derivative can preferably be derived from the compound of the group that is selected from vinylbenzene, ethene, propylene, iso-butylene or vinyl-acetic ester.As preferred monomer acrylic acid derivative, this extra building stone especially is derived from vinylformic acid or methyl acrylate.Preferred monomer methacrylic acid derivative is methacrylic acid, methyl methacrylate and methacrylic acid hydroxyethyl ester.
Here without limits, to the repeated structural unit number of multipolymer but verified particularly advantageous is that the adjustment structure unit number is so that multipolymer has the molecular-weight average of 1000-200000.
Second component of multipolymer is the oxyalkylene diols alkenyl ether, and it preferably uses with the amount of 40-55mol%.In preferred oxyalkylene diols alkenyl ether corresponding to formula V,
CH
2＝CR
3-(CH
2)
p-O-(C
mH
2mO)
n-R
1
V
R
3=H or have the aliphatic hydrocarbyl and the p=0-3 of 1-5 C atom.R
1, m and n have above-mentioned meaning.Here it is particularly advantageous having confirmed to use polyoxyethylene glycol mono vinyl ether (p=0 and m=2), and n preferably has the value of 2-15.
As being used to introduce building stone c to the present invention is vital) the 3rd component, preferably use ethene polyalkylene glycol, polysiloxane or the ester cpds of 1-5mol%.Use corresponding to the derivative of formula VI as preferred ethene polyalkylene glycol compounds,
Wherein S can preferred-H or-COOM
a, and U
1=-CO-NH-,-O-or-CH
2O-, acid amides, vinyl ether or the allyl ethers of promptly corresponding polypropylene glycol or polypropylene glycol-polyethyleneglycol derivative.
The x value is 0-150 and y=0-15.R
6Perhaps R
1Perhaps following structure:
U wherein
2=-NH-CO-,-O-and-OCH
2-, and S=-COOM
a, preferred-H.
If R
6=R
1And R
1During preferred H, then they are corresponding vinylformic acid (S=H, R
4=H), methacrylic acid (S=H, R
4=CH
3) or toxilic acid (S=COOM
a, R
4=H) polypropylene glycol of derivative (polyoxyethylene glycol) monoamide or ether.This monomeric example is toxilic acid N-(methyl polypropylene glycol) monoamide, toxilic acid N-(methoxyl group polypropylene glycol-polyoxyethylene glycol) monoamide, polypropylene glycol vinyl ether and polypropylene glycol allyl ethers.
If R
6≠ R
1, then they are difunctional vinyl compounds, its polypropylene glycol (polyoxyethylene glycol) derivative by amide group or ether (O-or-OCH
2-) be connected to each other.This examples for compounds is that polypropylene glycol-span comes amido acid, polypropylene glycol diacrylamine, polypropylene glycol DMAA, polypropylene glycol divinyl ether, polypropylene glycol diallyl ether.
Use is used as preferred ethene polysiloxane compound corresponding to the derivative of formula VII,
VII
R wherein
4=-H and CH
3,
W＝
And r=2-100 and preferred R
7=R
1This monomeric example is the mono-vinyl polydimethylsiloxane.
As other ethene polysiloxane compound, suitable derivative is corresponding to those of formula VIII,
Wherein s can=1 or 2, R
4Have above-mentioned meaning with W, and R
7Perhaps can=R
1Perhaps otherwise be following structure,
And the preferred hydrogen of S.
This has vinyl functional (R
7=R
1) monomeric example be the amino maleinamic acid of polydimethylsiloxane propyl group maleinamic acid or polydimethylsiloxane dipropylene.If R
7≠ R
1, then they are divinyl compounds, for example polydimethylsiloxane-two (propyl group maleinamic acid) or polydimethylsiloxane-two (the amino maleinamic acid of dipropylene).
As other ethene polysiloxane compound, suitable preferred derivative is corresponding to formula IX:
Wherein z can be 0-4 and R
4Or W has above-mentioned meaning.R
7Perhaps R
1Perhaps otherwise be following structure,
The preferred hydrogen of S wherein.This list vinyl compound (R
7=R
1) example be polydimethylsiloxane-(1-propyl group-3 acrylic acid ester) or polydimethylsiloxane-(1-propyl group-3-methacrylic ester).
If R
7≠ R
1, then they are divinyl compounds, for example polydimethylsiloxane-two (1-propyl group-3 acrylic acid ester) or polydimethylsiloxane-two (1-propyl group-3-methacrylic ester).
In the context of the invention, preferred use derivative corresponding to formula X as the vinyl acetate compound,
S=-COOM wherein
aOr-COOR
5And R
5Can be the aliphatic hydrocarbyl with 3-20 C atom, cyclic aliphatic alkyl and aryl with 6-14 C atom with 5-8 C atom.A and M have above-mentioned meaning.The example of this ester cpds is n-butyl maleate or di n butyl fumarate or positive butyl ester of toxilic acid list or the positive butyl ester of fumaric acid list.
In addition, also can use compound corresponding to formula XI,
Wherein z can be 0-4 and R
1Has known meaning.V can be W (being the polydimethylsiloxane base) in this case, and it is corresponding to dialkylene polydimethylsiloxane compound such as divinyl polydimethylsiloxane.Perhaps V also can be-O-CO-C
6H
4-CO-O-.These compounds are the derivative of dialkylene phthalic acid.The representative instance of this phthalic acid derivatives is a diallyl phthalate.
The molecular weight of compound formation building stone c) can change in very wide scope, and preferred 150-10000.
In addition, can make additionally 50mol% at the most, the vinyl of 20mol%, acrylic or methacrylic acid derivative carry out copolymerization especially at the most, and wherein said ratio is based on the monomer of the building stone of formula II, III and IV.As the monomer ethylene derivative, preferred vinylbenzene, ethene, propylene, iso-butylene or the vinyl-acetic ester of using, as the monomer acrylic acid derivative, preferred vinylformic acid or the methyl acrylate of using, and as the monomer methacrylic acid derivative, last preferred methacrylic acid, methyl methacrylate and the methacrylic acid hydroxyethyl ester of using.
Above-mentioned multipolymer is disclosed among the EP-A-736553.
Dispersion of the present invention can also contain its basis and be the multipolymer of oxidative olefinic diols (methyl) acrylate, and described multipolymer contains following building stone:
Type (a) monomer of 5-98 weight %, (alkoxyl group) polyalkylene glycol mono (methyl) acrylate of general formula X V,
Wherein,
R
1Be hydrogen atom or methyl,
R
2O is the oxyalkylene that a class has 2-4 carbon atom, and perhaps two classes or multiclass have the mixture of the oxyalkylene of 2-4 carbon atom, and supplementary condition are to add with two classes of mixture or multiclass or with block form or with random form,
R
3Be hydrogen atom or alkyl with 1-5 carbon atom and
M is the value of the average mol of the oxyalkylene that adds, and m is integer 1-200,
Type (b) monomer (methyl) vinylformic acid of the general formula X VI of 95-2 weight %,
Wherein,
R
4Be hydrogen atom or methyl, and M
1Be hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group,
And 0-50 weight can with other monomer (c) of these monomer copolymerizations, supplementary condition are that (a) and (b) and (c) total amount are 100 weight %.
Typical monomers (a) is:
(methyl) hydroxyethyl acrylate,
(methyl) vinylformic acid hydroxypropyl ester,
Polyethyleneglycol (methyl) acrylate,
Polypropylene glycol list (methyl) acrylate,
Polytetramethylene glycol list (methyl) acrylate,
Polyethylene glycol-propylene glycol list (methyl) acrylate,
Polyethylene glycol-butyleneglycol list (methyl) acrylate,
Polypropylene glycol-polytetramethylene glycol list (methyl) acrylate,
Polyethylene glycol-propylene glycol-polytetramethylene glycol list (methyl) acrylate,
Methoxy poly (ethylene glycol) list (methyl) acrylate,
Methoxyl group polypropylene glycol list (methyl) acrylate,
Methoxyl group polytetramethylene glycol list (methyl) acrylate,
Methoxy poly (ethylene glycol)-polypropylene glycol list (methyl) acrylate,
Methoxy poly (ethylene glycol)-polytetramethylene glycol list (methyl) acrylate,
Methoxyl group polypropylene glycol-polytetramethylene glycol list (methyl) acrylate,
Methoxy poly (ethylene glycol)-polypropylene glycol-polytetramethylene glycol list (methyl) acrylate,
Oxyethyl group polyethyleneglycol (methyl) acrylate,
Oxyethyl group polypropylene glycol list (methyl) acrylate,
The interior olefin(e) acid ester of oxyethyl group polytetramethylene glycol list (methyl),
Oxyethyl group polyethylene glycol-propylene glycol list (methyl) acrylate,
Oxyethyl group polyethylene glycol-butyleneglycol list (methyl) acrylate,
Oxyethyl group polypropylene glycol-polytetramethylene glycol list (methyl) acrylate,
Oxyethyl group polyethylene glycol-propylene glycol-polytetramethylene glycol list (methyl) acrylate.
Typical monomers (b) is: vinylformic acid and methacrylic acid, its monovalence and divalent metal salt, ammonium salt and/or organic amine salt.
Typical monomers (c) is: fatty alcohol and (methyl) acrylic acid ester with 1-20 C atom; Unsaturated dicarboxylic acid such as toxilic acid, fumaric acid, citraconic acid, its monovalence and divalent metal salt, ammonium salt and/or organic amine salt; Unsaturated dicarboxylic acid such as toxilic acid, fumaric acid, citraconic acid and have 1-20 C atom fatty alcohol, have 2-4 C atom glycol, add the monoesters or the diester of (alkoxyl group) polyalkylene glycol of the above-mentioned glycol of mole with 2-100; Unsaturated amides is as (methyl) acrylamide and (methyl) acryloyl alkylamine; Vinyl ester such as vinyl-acetic ester and propionate; Aromatic ethylene compound such as vinylbenzene; Unsaturated sulfonic acid is as (methyl) allyl sulphonic acid, (methyl) sulfoethyl acrylate, 2-methyl propane sulfonic acid (methyl) acrylamide (2-methylpropanesulfonic acid (meth) acrylamide), styrene sulfonic acid, its monovalence and divalent metal salt, ammonium salt and/or organic amine salt.
Another object of the present invention provides the method for preparing dispersion of the present invention, and it comprises a) or b) or c):
A) under agitation will be powder type or add in the initial aqueous silica dispersions as the polycarboxylate ether of the polycarboxylate ether aqueous solution, wherein said aggregate has the mean diameter less than 1 μ m, and optional water further dilutes this mixture,
B) SiO 2 powder is scattered in by suitable diverting device in the aqueous solution of polycarboxylate ether, optional subsequently water further dilutes,
C) SiO 2 powder is scattered in water, in the preferably water, subsequently in the aqueous solution with dispersions obtained adding polycarboxylate ether.The mixing of this dispersion in this case can be carried out under low-down shear energy, is for example undertaken by propeller stirrer.
Suitable diverting device is interpreted as following meaning: thus its energy input is enough to make silicon-dioxide to disperse to make aggregate to have less than those of the mean diameter of 1 μ m.
The dispersion of SiO 2 powder can be carried out in the equipment (for example dissolver, rotor-stator system) that will introduce system than low shear energy under minuent is filled.
Highly-filled in order to realize, must apply＞1000kJ/m
3Shear energy to obtain low viscous stable dispersion.High shear energy can for example be used ball milling, high-pressure homogenizer or the planet kneader of stirring and realize.
In addition, can advantageously use the method that is disclosed among the WO2005/063369, therein by pump, preferably at least two predispersion materials flows are sprayed onto on the impact point by high-pressure pump, spray in the milling zone that is surrounded by reactor chamber by a nozzle under each situation, this milling zone has overflowed predispersion and by the overvoltage that predispersion flow into milling zone it has been removed from milling zone.The method that is disclosed among the German patent specification DE10204470 is carried out in a similar manner.Here, by pump, preferably at least two predispersion materials flows are sprayed onto on the impact point by high-pressure pump, under each situation, spray in the reaction zone (reactor space) that surrounds by reactor chamber by a nozzle, and water vapor is introduced in the reaction zone by opening so that the steam in the reaction zone mainly is made up of water vapour, and by the overvoltage of the inflow water vapor of gas inlet side dispersion in small, broken bits and steam and/or partial condensation steam are removed from reaction zone, wherein said condensed steam mainly is made up of water.
Can choose diverting device such as the dissolver that use can obtain more low-yield input wantonly and at first produce predispersion.
Another object of the present invention is the purposes of dispersion of the present invention as concrete additive.
Another object of the present invention is the cement products that contains that contains dispersion of the present invention.
The preferred content of silicon-dioxide in containing cement products is that 0.01 weight % is to＜2 weight % based on cement.
Description of drawings
Fig. 1 is presented at that two kinds of BET surface-area are 90m in the dispersion of the present invention
2/ g and 200m
2The diameter Distribution of the silica aggregate of/g.
Fig. 2 shown in the dimension of cement sample CEM in J/g release energy in hour time relation.
Embodiment
Embodiment
Analyze: the numeric distribution of aggregate size (numerical distribution) is measured by dynamic light scattering, measuring apparatus: Horiba LB-500, useful range 0.003 μ m-6 μ m, number of iterations: 800.Relatively coarse meal P2 according to ISO13320-1 by laser diffraction measurement.
The BET surface-area is measured according to DIN66131.
The preparation of standard stucco (mortar) is carried out according to DIN EN196.Strength test is carried out being of a size of on the prism of 4 * 4 * 16cm according to DIN1164.
Parent material
Silicon-dioxide initial dispersions (SD):
SD1: in the stainless steel batch container (batchcontainer) with 32.5 kilograms of complete remollescent water addings 601.Under shearing condition, suck 17.5 kilograms AEROSIL90 then by the suction hose (stator slit: 4mm ring and 1mm ring, rotor/stator is apart from about 1mm) of Ystral Conti-TDS3.Subsequently, with mixture extra re-shearing 10min under 3000rpm.After grinding beginning, the pH of mixture is transferred to 10 with sodium hydroxide solution.The d of this silica dioxide granule
50Value is 154nm.The viscosity of dispersion is at 10s
-1Velocity of shear and 23 ℃ be down 6mPas.
SD2: in the stainless steel batch container (batchcontainer) with 32.5 kilograms of complete remollescent water addings 601.Under shearing condition, suck 17.5 kilograms AEROSIL 200 then by the suction hose (stator slit: 4mm ring and 1mm ring, rotor/stator is apart from about 1mm) of Ystral Conti-TDS 3.Subsequently, with mixture re-shearing 10min under 3000rpm.After grinding beginning, mixture is diluted to the concentration that is slightly larger than 20 weight % with complete remollescent water.Transfer to pH10 with sodium hydroxide solution.Then, add required remaining water to reach the silicon-dioxide ultimate density of 20 weight %.The d of this silica dioxide granule
50Value is 81nm.The viscosity of dispersion is at 10s
-1Velocity of shear and 23 ℃ be down 40mPas.
SD3: with 36 kilograms of complete remollescent water and 104g concentration is that 30% KOH solution adds in 601 the stainless steel batch container (batch container).Then by the silicon-dioxide that has sucked according to the doping of 16.5 kilogram of 0.44 weight % of DE19650500 preparation potassium from the dispersion of Ystral and inhaling type mixing tank (despenrsing and suction mixer) (at 4500rpm) and carry out pre-dispersed roughly.This predispersion is by from the assistance of rotor/stator flowing-type (flow-through) the homogenizer Z66 type of Ystral, and described homogenizer has the rotating speed of the wide and 3000rpm of four stator slit of handling ring, 1mm.After powder enters, use and under the rotating speed of 11500rpm, finish dispersion from the rotor/stator flowing-type homogenizer Z66 type of Ystral.This 15 minutes in the dispersion process under the 11500rpm, by adding other KOH solution pH regulator is 10.5 and keeps to pH.Here use other 779gKOH solution, and to regulate solids concn be 30 weight % by adding 1.5 kg water.With " wet blasting grinding machine ", from the Ultimaizer System of Sugino MachineLtd., model HJP-25050 under the pressure of 250Mpa and the diamond nozzles diameter be that the dispersion that 0.3mm and two mill roads (milling passage) will obtain is thus ground.The content of the doping silicon dioxide of this dispersion is 30 weight %.The d of this silica dioxide granule
50Value is 71nm.The viscosity of dispersion is at 500s
-1Velocity of shear and 23 ℃ be down 7.5mPas.
SiO 2 powder (P):
P4: pyrolysis SiO
2, the Li of 0.1 weight of having mixed
2O, specific surface area is 90m
2/ g
P5: precipitated silica, specific surface area are 165m
2/ g, mean aggregate diameter D
50(based on numeral): 5 μ m
P6: silica flour, specific surface area are 20m
2/ g, mean aggregate diameter D
50(based on numeral): 0.13 μ m polycarboxylate ether (PCE) is according to 2 preparations of embodiment among the EP-A-1189955, thereby amount carried out changing obtains 45% solution.
Dispersion (D):
D1 (according to the present invention): stir the following PCE aqueous solution (PCE content: 45 weight %) add among the SD1 of 1000g with 250g.
D2 (according to the present invention): stir the following PCE aqueous solution (PCE content: 45 weight %) add among the SD2 of 1000g with 183g.
D3 (according to the present invention): stir the following PCE aqueous solution (PCE content: 45 weight %) add among the SD3 of 1000g with 250g.
D4 (according to the present invention): the PCE aqueous solution (the PCE content: 45 weight %) that at first 3.2kg water is added 1000g.Be scattered in the PCE solution of dilution with the P1 of ball mill then 1400g.
D5 (Comparative Examples): the PCE aqueous solution (the PCE content: 45 weight %) that at first 4.4kg water is added 1000g.Be scattered in the PCE solution of dilution with the P5 of ball mill then 1100g.
D6 (Comparative Examples): the PCE aqueous solution (the PCE content: 45 weight %) that at first 2.9kg water is added 1000g.Be scattered in the PCE solution of dilution with the P6 of ball mill then 1750g.
Regulate the ratio of PCE and silicon-dioxide, thus when the dispersion adding is contained cement products, the content of silicon-dioxide based on cement content corresponding to 0.5 weight %.The initial flow metering of plaster be always 24+/-1cm.
The composition of this dispersion is shown in Table 1.D7 does not contain silicon-dioxide, but only contains PEC and be not dispersion.For clear, D7 still is shown in table 1.
Dispersion of the present invention does not significantly change on sedimentation stability and viscosity in during 6 months.
The preparation of standard stucco
Cement: CEI52.5 Mergelstetten, 20 ℃ of temperature.To add in the stucco blend corresponding to the dispersion of the dioxide-containing silica of 0.5 weight %, wherein said content is based on cement weight.The ratio of water/cement is 0.4 all the time.The results are summarized in the table 1.Gained surface early strength when having used dispersion of the present invention as a result significantly increases.
Test is carried out in calorimeter.As cement, used CEM I42.5 Bernburg.Use dispersion D1 of the present invention, D2 and D3.Add dispersion so that dioxide-containing silica is 0.5 weight % based on used cement.The proportions constant of water/cement is 0.5.With the dispersion D6 that contains " silica flour " with do not contain silicon-dioxide but the dispersion D7 that contains PCE compares.In used test, initial flow metering be 24+/-1cm.
Gained curve (Fig. 2) shown in the dimension of cement sample CEM in J/g release energy in hour time relation.Thermally developing is owing to the thermopositive reaction of cement mesosilicic acid salt face and water.This process is called cement hydration.The thermally developing of hydration reaction is big more in the concrete time at the most, and the intensity of the building part under this time is also high more usually.
This statement knows that demonstrating the plaster that adds dispersion of the present invention therein has higher reactivity.
Table 1: dispersion
*)The prismatical strength development of Zhi Bei plaster thus
| PCE | SiO 2 | PCE/ SiO 2 | The plaster prism | |||||
| Content weight % | Content weight % | BET surface-area m 2/g | Mean aggregate diameter μ m | Relative standard deviation % | Bend tension intensity N/mm behind the 8h 2 | Ultimate compression strength N/mm behind the 8h 2 | ||
| D1 | 9 | 28 | 90 | 0.18 $) | 23 | 0.32 | 3.44 | 13.35 |
| D2 | 7 | 17 | 200 | 0.09 §) | 25 | 0.41 | 3.29 | 13.12 |
| D3 | 9 | 24 | 88 | 0.21 | 22 | 0.38 | - | 14.82 |
| D4 | 8 | 25 | 99 | 0.18 | 24 | 0.32 | - | 13.72 |
| D5 | 7 | 17 | 165 | 1.50 | - | 0.41 | - | 8.81 |
| D6 | 8 | 31 | 20 | 0.13 | - | 0.26 | - | 9.12 |
| |
30 | 0 | - | - | - | - | 2.39 | 8.64 |
*) D1-D4: according to the present invention; D5-D7: Comparative Examples;
Claims (16)
1, a kind of dispersion, it does not contain tackiness agent and contains silicon-dioxide and at least a water soluble polycarboxylic acid ester ether, wherein
-described silicon-dioxide is pyrolytic silicon dioxide, and it is, and gathering primary granule form exists and the BET surface-area is 50-250m
2/ g, wherein
Aggregate in the-dispersion has the mean diameter less than 1 μ m, and
The ratio of-silicon-dioxide is 5-50 weight % based on the dispersion total amount,
-described water soluble polycarboxylic acid ester ether is based on the multipolymer of at least a oxyalkylene diol compound and at least a unsaturated monocarboxylic derivative or dicarboxylic acid derivatives,
The weight ratio of-polycarboxylate ether/silicon-dioxide is 0.01-100.
2, dispersion as claimed in claim 1, wherein said pyrolytic silicon dioxide comprise and contain silicon-dioxide as first component and Lithium Oxide 98min, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, aluminum oxide or the zirconium dioxide mixed oxide as second component.
3, as the dispersion of claim 1 or 2, the aggregate in the wherein said dispersion has the mean diameter of 50-500nm.
4, as each dispersion among the claim 1-3, the relative standard deviation of the numeric distribution of the aggregate diameter of wherein said silicon-dioxide is less than 30%.
5, as each dispersion among the claim 1-4, the ratio of silicon-dioxide is total up to 10-30 weight % based on the dispersion total amount in the wherein said dispersion.
6, as each dispersion among the claim 1-5, the weight ratio of wherein said polycarboxylate ether/silicon-dioxide is 0.05-5.
7, as each dispersion among the claim 1-6, the pH of wherein said dispersion is 8-12.
8, as each dispersion among the claim 1-7, the basis of wherein said multipolymer is an oxidative olefinic diols alkenyl ether, and described multipolymer contains following building stone:
A) building stone of the formula Ia of 25-95mol% and/or Ib and/or Ic,
Wherein
R
1=hydrogen or have the aliphatic hydrocarbyl of 1-20 C atom,
X＝-OM
a、-O-(C
mH
2mO)
n-R
2、-NH-(C
mH
2mO)
n-R
2，
M=hydrogen, monovalence or divalent metal, ammonium ion, organic amino group,
A=1/2 or 1,
R
2=hydrogen, aliphatic hydrocarbyl, cyclic aliphatic alkyl, the optional aryl that replaces with 6-14 C atom with 5-8 C atom with 1-20 C atom,
Y＝O、NR
2，
M=2-4 and n=0-200,
B) building stone of 1-48.9mol% general formula I I,
Wherein
R
3Be hydrogen or aliphatic hydrocarbyl with 1-5 C atom,
P be 0-3 and,
R
2, m and n and have above-mentioned meaning,
C) the formula III a of 0-5mol% or the building stone of IIIb,
Wherein S=-H ,-COOM
a,-COOR
5
T＝-U
1-(CH(CH
3)-CH
2-O)
x-(CH
2-CH
2-O)
y-R
6
-W-R
7
-CO-[NH-(CH
2)
3]
s-W-R
7
-CO-O-(CH
2)
z-W-R
7
-(CH
2)
z-V-(CH
2)
z-CH＝CH-R
2
-COOR
5, if S=-COOR
5Or-COOM
aThe time,
U
1＝-CO-NH-、-O-、-CH
2O-
U
2＝-NH-CO-、-O-、-OCH
2-
V=-O-CO-C
6H
4-CO-O-or-W-
R
4＝H、CH
3
R
5=have 3-20 carbon atom aliphatic hydrocarbyl, have 5-8 C atom the cyclic aliphatic alkyl, have the aryl of 6-14 C atom,
R
6＝R
2，
R
7＝R
2，
r＝2-100
s＝1，2
z＝0-4
x＝1-150
y＝0-15
With,
D) the general formula I Va of 0-47.9mol and/or the building stone of IVb,
Wherein a, M, X and Y have above-mentioned meaning.
9, dispersion as claimed in claim 8, wherein said multipolymer contain the formula Ia of 51-95mol% and/or building stone and the formula III a of 0.1-5mol% or the building stone of IIIb of Ib and/or Ic.
10, as each dispersion among the claim 1-7, the basis of wherein said multipolymer is an oxidative olefinic diols alkenyl ether, and described multipolymer contains following building stone:
A) building stone of the formula IVa of 10-90mol% and/or IVb,
Wherein
M=hydrogen, monovalence or divalent metal, ammonium ion, organic amino group,
A=1 is to be 1/2 under the situation of divalent-metal ion at M perhaps,
X also=-OM
aOr
-O-(C
mH
2mO)
n-R
1, R wherein
1=H, aliphatic hydrocarbyl, cyclic aliphatic alkyl, the optional aryl that replaces with 6-14 C atom with 5-8 C atom with 1-20 C atom,
m＝2-4，
n＝0-200，
-NHR
2And/or-NR
2 2, R wherein
2=R
1Or-CO-NH
2, and
Y＝O、NR
2
B) building stone of the formula II of 1-89mol%,
R wherein
3=H, have the aliphatic hydrocarbyl of 1-5 C atom,
p＝0-3
And R
1, m, n have above-mentioned meaning, and
C) the formula III a of 0-10mol% or the building stone of IIIb,
Wherein
S＝-H、-COOM
a、-COOR
5
-W-R
7
-CO-[NH-(CH
2)
3]
s-W-R
7
-CO-O-(CH
2)
z-W-R
7
-(CH
2)
z-V-(CH
2)
z-CH＝CH-R
1
-COOR
5, if S=-COOR
5Or-COOM
aThe time,
U
1＝-CO-NH-、-O-、-CH
2O-
U
2＝-NH-CO-、-O-、-OCH
2
V=-O-CO-C
6H
4-CO-O-or-W-
W＝
R
4＝H、CH
3
R
5=have 3-20 C atom aliphatic hydrocarbyl, have 5-8 C atom the cyclic aliphatic alkyl, have the aryl of 6-14 C atom,
R
6＝R，
r＝2-100，
s＝1，2，
z＝0-4，
x＝1-150，
y＝0-15。
11, as the dispersion of claim 10, wherein said multipolymer contains the formula III a of 0.1-10mol% or the building stone of IIIb.
12, as each dispersion among the claim 1-7, the basis of wherein said multipolymer is oxidative olefinic diols (methyl) acrylate, and described multipolymer contains following building stone:
Type (a) monomer of 5-98 weight %, (alkoxyl group) polyalkylene glycol mono (methyl) acrylate of general formula X V,
Wherein
R
1Be hydrogen atom or methyl,
R
2O is the oxyalkylene that a class has 2-4 carbon atom, and perhaps two classes or multiclass have the mixture of the oxyalkylene of 2-4 carbon atom, and condition is the mixture of two classes or multiclass can be added with block form or with random form,
R
3Be hydrogen atom or alkyl with 1-5 carbon atom and
M is the mean value of the adding mole number of oxyalkylene, and m is integer 1-200,
The monomer of (methyl) acrylic-type (b) of 95-2 weight % general formula X VI,
Wherein
R
4Be hydrogen atom or methyl, and M
1Be hydrogen atom, monovalence atoms metal, divalent metal atom, ammonium or organic amino group,
And 0-50 weight can with other monomer (c) of these monomer copolymerizations, condition is that (a) and (b) and (c) total amount are 100 weight %.
13, a kind of preparation is as the method for each dispersion among the claim 1-12, and it comprises:
A) under agitation will be powder type or add in the initial aqueous silica dispersions as the polycarboxylate ether of the polycarboxylate ether aqueous solution, wherein said aggregate has the mean diameter less than 1 μ m, and optional water further dilutes this mixture, perhaps
B) SiO 2 powder is scattered in by suitable diverting device in the aqueous solution of polycarboxylate ether, optional subsequently water further dilutes, perhaps
C) SiO 2 powder is scattered in water, the preferably water, subsequently in the aqueous solution with dispersions obtained adding polycarboxylate ether.
14, as each dispersion among the claim 1-13 as the purposes of concrete additive.
15, a kind of comprise as among the claim 1-14 each dispersion contain cement products.
16, as the cement products that contains of claim 17, wherein said concrete mix contains the silicon-dioxide of 0.01 weight % to＜0.2 weight % based on cement.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006005093A DE102006005093A1 (en) | 2006-02-04 | 2006-02-04 | Silica and polycarboxylate ether-containing dispersion |
| DE102006005093.2 | 2006-02-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101081920A true CN101081920A (en) | 2007-12-05 |
| CN101081920B CN101081920B (en) | 2012-03-21 |
Family
ID=38057553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100077906A Expired - Fee Related CN101081920B (en) | 2006-02-04 | 2007-02-02 | Dispersion comprising silicon dioxide and polycarboxylate ether |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1981823A1 (en) |
| CN (1) | CN101081920B (en) |
| DE (1) | DE102006005093A1 (en) |
| WO (1) | WO2007088111A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904860A (en) * | 2017-01-22 | 2017-06-30 | 上海每天生态科技发展有限公司 | A kind of nano inorganic reinforcing agent |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006049524A1 (en) | 2006-10-20 | 2008-04-24 | Evonik Degussa Gmbh | Aqueous dispersions of precipitated silicas and silicates to increase the early strength in cementitious preparations |
| DE102007046745A1 (en) | 2007-09-28 | 2009-04-02 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Disperse dye and / or UV absorber containing preparations |
| DE102008017251B9 (en) † | 2008-04-04 | 2009-11-26 | Xella Technologie- Und Forschungsgesellschaft Mbh | Process for the production of aerated concrete and foam concrete and plant for carrying out the process |
| CN102303980B (en) * | 2011-07-04 | 2013-03-20 | 湘潭宏远工程材料科技有限公司 | DPS (Deep Penetrating Sealer) contacting permeation type waterproof and anticorrosion coating and production process thereof |
| EP2917279B1 (en) | 2012-11-09 | 2016-12-14 | Sika Technology AG | Polycarboxylate ether as dispersion agent for epoxy resins |
| ES2545303B1 (en) * | 2015-05-12 | 2016-03-08 | Alfonso Javier MORAÑO RODRÍGUEZ | Addition to obtain structural concrete and thermal conductive mortars |
| CN115872668B (en) * | 2022-12-28 | 2024-02-20 | 科之杰新材料集团有限公司 | Composite retarding polycarboxylate superplasticizer and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9603418D0 (en) * | 1996-09-19 | 1996-09-19 | Eka Chemicals Ab | A method of preparation of a hardening composition |
| DE19926611A1 (en) * | 1999-06-11 | 2000-12-14 | Sueddeutsche Kalkstickstoff | Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and oxyalkylene glycol alkenyl ethers, process for their preparation and their use |
| TW527332B (en) * | 2000-05-19 | 2003-04-11 | Akzo Nobel Nv | Composition and method to prepare a concrete composition |
| FR2815629B1 (en) * | 2000-10-25 | 2003-09-05 | Coatex Sas | PROCESS FOR IMPROVING MECHANICAL RESISTANCE IN PARTICULAR "TO THE YOUNG AGES" OF CEMENT MATRICES, CEMENT MATRICES OBTAINED AND THEIR USES |
| DE10146325A1 (en) * | 2001-09-20 | 2003-04-10 | Degussa | Precipitated silica with a high BET / CTAB ratio |
| US6858074B2 (en) * | 2001-11-05 | 2005-02-22 | Construction Research & Technology Gmbh | High early-strength cementitious composition |
| DE10258857A1 (en) * | 2002-12-17 | 2004-07-08 | Degussa Ag | Fumed silica and dispersion thereof |
| EP1477457B1 (en) * | 2003-05-14 | 2007-07-25 | Degussa GmbH | Surface modified precipitated silica |
| EP1607378A1 (en) * | 2004-06-18 | 2005-12-21 | Degussa AG | Cement composition comprising fumed metal oxide powder |
| DE102004032399A1 (en) * | 2004-07-03 | 2006-02-09 | Construction Research & Technology Gmbh | Blend composition containing copolymers based on unsaturated carboxylic acid and alkenyl ether derivatives and sulfo-containing copolymers and terpolymers |
-
2006
- 2006-02-04 DE DE102006005093A patent/DE102006005093A1/en not_active Ceased
-
2007
- 2007-01-19 WO PCT/EP2007/050544 patent/WO2007088111A1/en active Application Filing
- 2007-01-19 EP EP07704014A patent/EP1981823A1/en not_active Withdrawn
- 2007-02-02 CN CN2007100077906A patent/CN101081920B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904860A (en) * | 2017-01-22 | 2017-06-30 | 上海每天生态科技发展有限公司 | A kind of nano inorganic reinforcing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1981823A1 (en) | 2008-10-22 |
| WO2007088111A1 (en) | 2007-08-09 |
| DE102006005093A1 (en) | 2007-08-09 |
| CN101081920B (en) | 2012-03-21 |
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