CN101028972A - Building material mixture additive containing solid microparticle - Google Patents
Building material mixture additive containing solid microparticle Download PDFInfo
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- CN101028972A CN101028972A CN200610081746.5A CN200610081746A CN101028972A CN 101028972 A CN101028972 A CN 101028972A CN 200610081746 A CN200610081746 A CN 200610081746A CN 101028972 A CN101028972 A CN 101028972A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
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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
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
- C04B16/085—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons expanded in situ, i.e. during or after mixing the mortar, concrete or artificial stone 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
- 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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0049—Water-swellable polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0058—Core-shell polymers
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Abstract
The present invention relates to the use of compact polymeric microparticles in hydraulically setting building material mixtures for improving their resistance to freezing or to freeze/thaw cycles.
Description
The present invention relates to polymeric microsphere and in the hydraulicity building material mixture, be used to improve the alternating purposes of its frost resistance or anti-freeze-melt.
Concrete is defined as artificial stone as important material of construction according to DIN 1045 (07/1988), and it is also contained concrete admixture and concrete admixture in case of necessity and formed by sclerosis by cement, aggregate and water.Concrete especially is divided into intensity groups (BI-BII) and strength grade (B5-B55).When mixing formation gas or foamy material, form cellular concrete or foamed concrete (R mpp Lexikon, the 10th edition, 1996, Georg Thieme press).
Concrete has two performances that rely on the time.The first, it experiences a volume owing to becoming dry and reduces, and is called contraction.But most water is combined into crystal water.Concrete does not have drying, and it solidifies, and promptly at first is cementing glue (cement and the water) hardening of thin liquid attitude, solidifies and becomes hard at last, and this depends on that it is the moment and the process of hydration that chemistry-mineralogy of cement and water reacts.Because cement is to the binding ability of water, concrete is opposite with lime kilning also can to harden under the effect of water and keeps hard.The second, concrete can be out of shape promptly so-called creep under the load effect.
Freeze-melt alternately to be meant that the weather in the freezing point left and right sides of water temperature replaces.Particularly under mineral bonded material of construction such as concrete situation, freezing-melting alternately is a kind of damage mechanism.This material has the porous capillary pipe structure, is not watertight.If a kind of such structure that is soaked in water suffers the temperature below 0 ℃, then water can be frozen in the hole.Because the density abnormality of water, at this moment ice can expand.Therefore material of construction occurring damages.In very thin hole,, freezing point reduces because can appearring in surface effects.In micropore, water is just freezing below-17 ℃.Because material itself can produce the kapillary pump in addition and inhale effect owing to freeze-melt alternately also can to expand and shrink, it has further improved the absorption of water and has further improved damage thus indirectly.Therefore, freezing-melt the alternative number is conclusive for damaging.
Freeze and anti-freeze-thawing alternative resistibility for concrete opposing under the effect in melting agent, the density of concrete weave construction, the situation that exists that structure is formed in certain intensity of matrix and certain hole is conclusive.The concrete weave construction of cement bonded by pore (radius: 2 μ m-2mm) or gel pore (radius: 2-50nm) institute interlacing.Wherein the pore water that is contained is different according to bore dia and on its stastus format.Although the water in the pore has kept its common character, but in gel pore according to water of condensation (mesopore: 50nm) and absorption bonded surface water (micropore: 2nm) classify, their freezing point for example can be well below-50 ℃ of [M.J.Setzer, Interaction of water with hardened cementpaste (interaction of water and petrifying water clay coating), " Ceramic Transactions " 16 (1991) 415-39].Such result is even that when the concrete degree of depth is cooled off, a part of pore water also keeps not freezing (meta water).But under identical temperature, Fang vapour pressure is less than side's waterborne vapour pressure on ice.Because ice and meta water are deposited simultaneously also, will form the vapour pressure drop, it causes still taking place thus to gather than the dehydration of aperture or than icing in the macropore for the water of liquid causes and it forms ice to the ice diffusion.It is this because the water redistribution that cooling causes occurs in the type that also depends on pore distribution in each punctulate system fatefully.
The fine airport of artificial importing also at first produces so-called discharge space for swelling property ice or frozen water in concrete.In these holes, the pore water that freezes may expand or block the ice and the interior pressure and the stress of frozen water, does not freeze destruction and cause that tiny crack forms and causes thus aspect concrete.The mode of action on this airport system principle and concrete freeze failure mechanisms and are described [Schulson in a large amount of summaries explicitly, Erland M. (1998), Ice damage to concrete (ice is to concrete damage), CRREL Special Report98-6; S.Chatterji, Freezing of air-entrained cement-basedmaterials and specific actions of air-entraining agents (cement-based material of entrapped air freeze specific function with air entrainment agent), " Cement ﹠amp; Conerete Composites " 25 (2003) 759-65; G.W.Scherer, J.Chen ﹠amp; J.Valenza, Methods for protecting concrete from freeze damage (the protection concrete is avoided the method for freezing damage), US patent 6,485,560 B1 (2002); M.Pigeon, B.Zuber ﹠amp; J.Marchand, Freeze/thaw resistance (anti-freezing/melting property), " Advanced Concrete Technology " 2 (2003) 11/1-11/17; B.Erlin ﹠amp; B.Mather, A new process by which cyclic freezing candamage concrete-the Erlin/Mather effect (circulation freeze can so as to damaging concrete new process-Erlin/Mather effect), " Cement ﹠amp; ConcreteResearch " 35 (2005) 1407-11].
Precondition for the stability of concrete improvement in freezing-melting alternately is, the distance in every bit and nearest artificial air hole is no more than certain value in the cement brick.This distance is also referred to as apart from the factor or " Powers interval factor " [T.C.Powers, The airrequirement of frost-resistant concrete (the concrete api request of resistance and freeze), " Proceedings of the Highway Research Board " 29 (1949) 184-202].At this, the laboratory is detected and is shown, critical " the Power interval factor " that surpass 500 μ m can cause concrete to destroy in freezing and melting alternately.In order to realize this condition under restricted airport content, the diameter of manually-injected airport therefore must be less than 200-300 μ m[K.Snyder, K.Natesaiyer ﹠amp; K.Hover, Thestereological and statistical properties of entrained air voidsin concrete:A mathematical basis for air void systemscharacterization (the three-dimensional logic and the statistic property of the air void of carrying secretly in the concrete: the Fundamentals of Mathematics of air void diagram of system requisition)) " Materials Science ofConcrete " VI (2001) 129-214].
The type of the composition of aggregate and particle shape (Formit t), cement and consumption, concrete consistence, the mixing tank of use, mixing time, temperature are depended in the formation of artificial air's pore system fatefully, and the type of air pore-forming agent and consumption.Considering under the corresponding production adjusting situation, but although their influence Be Controlled, but can produce a large amount of undesirable damages, desirable air content also has a negative impact to concrete intensity or frost resistance in the concrete thereby this finally causes surpassing or not reaching.
Such artificial air hole cannot directly be metered into, but by adding the stable in addition [L.Du of air that so-called air pore-forming agent will be brought into by mixing; K.J.Folliard, Mechanism of air entrainment in concrete (the entrained air mechanism in the concrete) " Cement ﹠amp; Concrete Research " 35 (2005) 1463-71].Traditional air pore-forming agent major part is the structure of tensio-active agent sample and will be broken into diameter by the air of mix introducing as far as possible less than the little air filled cavity of 300 μ m, and it is stabilized in the moist concrete weave construction.At this, divide into two types.
One type-for example sodium salt or the Vinsol resin (Vinsolharz) of sodium oleate, sylvic acid, a kind of extract of pine root-with the cement viscose glue in the calcium hydroxide reaction of hole solution, and go out as insoluble calcium precipitation.This hydrophobicity salt has reduced the surface tension of water and has accumulated between cement particle, the empty G﹠W at the interface.They are with micro-bubble stabilization and the surface that therefore is positioned at these airports in the hardened concrete once more.
Sodium Lauryl Sulphate BP/USP (SDS) of another kind of type-for example or dodecylphenyl sodium sulfonate-form soluble calcium salt with calcium hydroxide on the contrary, but it demonstrates unusual solubility behavior.Under certain critical temperature, this tensio-active agent demonstrates very low solvability, and it has very good solubility when being higher than this temperature.By preferably accumulating in air-water interface layer place, they have reduced surface tension equally, thereby have stablized micro-bubble and the preferred surface that is positioned at this airport in the hardened concrete once more.
When using this air pore-forming agent according to prior art, a large amount of problem [L.Du has appearred; K.J.Folliard, Mechanism of air entrainment in concrete " Cement ﹠amp; Concrete Research " 35 (2005) 1463-71].For example, long mixing time, different mixing tank revolution, the process that is metered into that changes when the transportation concrete air (in airport) that may cause being stabilized is overflowed once more.
With the haulage time that prolongs, the temperature adjustment and the different pumping and the e Foerderanlage transportation concrete of difference, and introduce aftertreatment, the shake that this concrete and the consequent change and wash in a pan (Ruckel) behavior and temperature condition, may change the airport content of previous adjusting significantly.This may mean in the worst case, thereby no longer satisfying the needed ultimate value of certain levels of exposure, concrete can not use [EN 206-1 (2000) with becoming, Concrete-Part 1:Secification, performance, production and conformity].
The content (cement that for example has Different Alkali content, additive such as flying dust, silica dust or color additive) of thin material hinders airport to form equally in the concrete.Interaction with the flowing agent of froth breaking effect also may take place, and therefore this flowing agent drives out airport, but also may additionally controllably not introduce.
Improving the alternating newer possible method of frost resistance and anti-freeze-thawing is, by sneaking into or solid is metered into polymeric microsphere (little hollow ball) and reaches this air content [H.Sommer, A new method of making concrete resistant to frostand de-icing salts (a kind of novel method and ice-removal salt that makes concrete antifreezing), " Betonwerk ﹠amp; Fertigteiltechnik " 9 (1978) 476-84].Because the micropartical major part has granularity less than 100 μ m, thus they in the concrete weave construction can in addition the thinner and distribution more equably than manually-injected airport.Thereby, just enough be used for concrete abundant anti-freeze on a small quantity and melt exchange.It has been known [referring to DE 2229094 A1, US 4,057,526 B1, US 4,082,562 B1, DE3026719 A1] according to prior art that this polymeric microsphere is used to improve concrete anti-freeze and the alternating application of anti-freeze-thawing.Wherein the micropartical of Miao Shuing especially is characterised in that, they have a cavity and a this hollow core less than 200 μ m (diameter) and are made up of air (or gaseous substance).This has comprised small porous particle of 100 μ m yardsticks equally, and they may have many more areola and/or hole.
Closely knit polymeric microsphere considers to be used to improve frost resistance so far hardly and anti-freeze-thawing replaces property.
But for little hollow ball, need higher dosage, reaching the value of subcritical " Power interval factor ", this is that big particle dia by＞100 μ m causes at least in part.This true combination with the high production cost that is caused by the multistep preparation method influences the enforcement of this technology on market unfriendly.
Therefore task of the present invention is, building material mixture a kind of who is provided for hydraulicity improves the alternating reagent of frost resistance or anti-freeze-melt, and renders a service completely and can simply and cheaply prepare in addition even it has also brought into play it under lower dosage.Another task is to damage or can significantly not damage the physical strength of building material mixture by this reagent.
Find unexpectedly now, even frost resistance or anti-freeze-thawings that single level or the multi-level closely knit polymeric microsphere that constitutes also are suitable for improving the building material mixture that is used for hydraulicity replace property.The micropartical that single level constitutes is meant to form goes up the particle (no shell) that evenly constitutes.Do not have air to be brought in the building material mixture, so this is more unexpected by this polymeric microsphere.
The mode of action can be as the following explanation that makes an explanation: polymeric microsphere according to the present invention is evenly distributed in the building material mixture.Hole between micropartical and hardened building material mixture, optionally because building material mixture shrinks and also increase constantly in sclerosis, this hole is as the expansion place of freezing water for it.This average headway that has each other is used to improve alternately property of frost resistance or anti-freeze-thawing then less than the uniform distribution in the capillary activity hole of " Power interval factor ".
By using according to forming polymer body of the present invention, the air that enters in the building material mixture can keep lowly especially.Thus, realized the ultimate compression strength of concrete obvious improvement.Like this, can realize in other cases can only be by the adjustable strength grade of significantly reduced water/cement value (W/Z value).But low W/Z value again may the concrete processibility of significant limitation.High compression strength also is favourable and especially owing to be used in concrete that intensity forms that needed cement content can reduce but significant, thereby the price of every cubic meter of concrete can descend significantly.
Polymeric microsphere comprises at least a monoene and belongs to unsaturated monomer.Micropartical can be a single level or multi-level, and comonomer wherein at all levels is formed can be different.Preferably especially comprise (methyl) acrylic acid nitrile and other nitrogenous methacrylic ester, as the methacrylamido acetonitrile, 2-methacryloxyethyl methyl cyanamide, methacrylic acid cyano methyl ester; The methacrylic ester that contains carbonyl, as, methacrylic acid oxazolidinyl ethyl ester, N-(methacryloxy) methane amide, methacrylic acid acetonyl ester, N-methacryloyl morpholine, N-methacryloyl-2-Pyrrolidone; The dimethacrylate diol ester, as methacrylic acid 1, the 4-butanediol ester, methacrylic acid 2-butoxy ethyl ester, methacrylic acid 2-ethoxy ethoxy methyl ester, methacrylic acid 2-ethoxyethyl group ester, the methacrylic ester of ether alcohol is as the methacrylic acid tetrahydro furfuryl ester, methacrylic acid vinyl oxygen base oxethyl ethyl ester, methacrylic acid methoxy base oxethyl ethyl ester, methacrylic acid 1-butoxy propyl diester, methacrylic acid 1-methyl-(2-vinyl oxygen base) ethyl ester, methacrylic acid cyclohexyl oxygen ylmethyl ester, methacrylic acid methoxymethoxy ethyl ester, methacrylic acid benzyl oxygen ylmethyl ester, methacrylic acid furfuryl group ester, methacrylic acid 2-butoxy ethyl ester, methacrylic acid 2-ethoxy ethoxy methyl ester, methacrylic acid 2-ethoxyethyl group ester, methacrylic acid allyloxy methyl ester, methacrylic acid 1-oxyethyl group butyl ester, methacrylic acid methoxy ylmethyl ester, methacrylic acid 1-ethoxyethyl group ester, methacrylic acid ethoxyl methyl ester; Methacrylic acid epoxy alkyl ester, as methacrylic acid 2,3-epoxy group(ing) butyl ester, methacrylic acid 3,4-epoxy group(ing) butyl ester, glycidyl methacrylate; The methacrylic ester that contains phosphorus, boron and/or silicon, as methacrylic acid 2-(the dimethyl phosphoric acid ester is closed (phosphato)) propyl diester, methacrylic acid 2-(ethylidene (phosphorous acid ester closes) (phosphito)) propyl diester, dimethylaminoethyl acrylate methyl base phosphinomethyl ester, dimethylaminoethyl acrylate methyl base phosphonoethyl ester, diethylmethyl acryl phosphonic acid ester, dipropyl methacryloyl phosphoric acid ester; The methacrylic ester of sulfur-bearing, as methacrylic acid ethyl sulfinyl ethyl ester, methacrylic acid 4-thiocyanato butyl ester, methacrylic acid ethylsulfonyl ethyl ester, methacrylic acid thiocyanato methyl ester, methacrylic acid methyl sulfinyl methyl ester, two (methacryloxyethyl) sulfide;
Vinyl ester is as vinyl-acetic ester;
Vinylbenzene contains the substituted phenylethylene of alkyl substituent at side chain, and for example * vinyl toluene and * ethyl styrene contain the substituted phenylethylene of alkyl substituent, as Vinyl toluene and p-methylstyrene on ring;
The heterocyclic vinyl compound, as the 2-vinyl pyridine, the 3-vinyl pyridine, 2-methyl-5-vinylpyrine, 3 ethyls-4-vinylpridine, 2,3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, vinyl piperidines, 9-vinylcarbazole, the 3-vinylcarbazole, the 4-vinylcarbazole, 1-vinyl imidazole, 2-methyl isophthalic acid vinyl imidazole, the N-vinyl pyrrolidone, the 2-vinyl pyrrolidone, N-ethenyl pyrrolidone, 3-ethenyl pyrrolidone, the N-caprolactam, the N-vinyl butyrate lactam, vinyl tetrahydrofuran (oxolan), vinyl furans, the vinyl thiophene, vinyl thiacyclopentane (thiolan), vinylthiazole and hydrogenant vinylthiazole, vinyl azoles and hydrogenant vinyl azoles;
Vinyl ether and prenyl ether;
Maleic acid derivatives, as the diester of toxilic acid, wherein alcohol groups has 1-9 carbon atom, maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide;
Fumaric acid derivatives, as the diester of fumaric acid, wherein alcohol groups has 1-9 carbon atom;
Alpha-olefin such as ethene, propylene, n-butene, iso-butylene, positive amylene, isopentene, n-hexylene, dissident's alkene; Tetrahydrobenzene.
Find in addition, except ion exclusion, can realize also that by corresponding monomer the solid space of forming polymer body repels.This has caused the additional stabilization of forming polymer body in dispersion and building material mixture.
Therefore, according to the present invention, also can use the molar mass that has hydrophilic radical monomer greater than the free redical polymerization of 200g/mol.Particularly preferably be and have a monomer that contains the polyoxyethylene blocks of two or more oxygen ethylene unit.The preferred use is selected from methoxy poly (ethylene glycol) CH
3O (CH
2CH
2O)
n(methyl) acrylate of H (wherein n 〉=2), (methyl) acrylate of the C16-C18-fatty alcohol mixture of ethoxylation (containing two or more oxygen ethylene unit), the methacrylic ester of uncle's 5-octylphenoxy polyethoxy ethanol (containing two or more oxygen ethylene unit), the monomer of Nonylphenoxy polyethoxyethanols (containing two or more oxygen ethylene unit) or their mixture.
In addition, can contain one or more monoene that have acidic group and belong to unsaturated monomer.Vinylformic acid preferably, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan, alpha-cyanoacrylate is to methacrylic acid (Ba Dousuan), α-Ben Jibingxisuan, to acryloxy propionic, Sorbic Acid, α-chlorine Sorbic Acid, 2 '-the methyl iso-crotonic acid, styracin, to chloro-cinnamic acid, to stearic acid, methylene-succinic acid, citraconic acid, methylfumaric acid, propene dicarboxylic acid, equisetic acid, toxilic acid, fumaric acid, three carboxyl ethene and maleic anhydrides, the hydroxyl of above-mentioned acid or amino ester, preferred acrylic or methacrylic acid, as vinylformic acid 2-hydroxyethyl ester, vinylformic acid N, the like derivatives of N-dimethyl aminoethyl ester and methacrylic acid, wherein vinylformic acid and methacrylic acid be particularly preferred and in addition vinylformic acid be preferred.
Except the monoene that contains acidic group belongs to the unsaturated monomer, this polymkeric substance also can belong to the different comonomer of unsaturated monomer based on other the monoene with containing acidic group.As comonomer olefinic unsaturated sulfonic acid monomer preferably, unsaturated phosphonic acids monomer of olefinic and acrylamide.
Olefinic unsaturated sulfonic acid monomer is the sulfonic acid of aliphatics or aromatic ethenyl sulfonic acid or acrylic acid or the like or methacrylic preferably.As aliphatics or aromatic ethenyl sulfonic acid preferably vinyl sulfonic acid, allyl sulphonic acid, 4-vinyl benzyl sulfonic acid, vinyl toluene sulfonic acid and styrene sulfonic acid.As acrylic or methacryloyl sulfonic acid sulfoethyl acrylate preferably; methacrylic acid sulfoethyl ester; vinylformic acid sulfopropyl ester, methacrylic acid sulfopropyl ester, 2-hydroxy-3-methyl acryloxy propyl sulfonic acid and 2-acrylamide-2-methyl propane sulfonic acid.
The unsaturated phosphonic acids monomer of olefinic, as vinyl phosphonate, allyl group phosphonic acids, vinyl benzyl phosphonic acids, acrylamido alkyl phosphonic acid, acrylamido alkyl di 2 ethylhexyl phosphonic acid, (phosphonomethyl) vinyl amine, (methyl) acryl phosphonate derivative.
Possible acrylamide is an AAM, or the derivative of the aminoalkyl group of acrylamide or Methacrylamide replacement, as the N-vinylamide, the N-vinyl formamide, the N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylformamide, N-methylol (methyl) acrylamide, vinyl pyrrolidone, N, N-dimethyl propyl acrylamide, DMAA or diethyl acrylamide and corresponding methacrylamide derivatives and acrylamide and Methacrylamide, wherein preferred acrylamide.
Chemically crosslinked realizes by well known to a person skilled in the art linking agent.This linking agent may reside in each level.Preferred cross-linking agents is polyacrylic ester or polymethacrylate according to the present invention, it for example passes through polyvalent alcohol or ethoxylation polyvalent alcohol such as ethylene glycol, propylene glycol, TriMethylolPropane(TMP), 1, and 6-hexylene glycol glycerine, tetramethylolmethane, polyoxyethylene glycol or polypropylene glycol and acrylic or methacrylic acid-respons obtain.Also can use polyvalent alcohol, amino alcohol and their list (methyl) acrylate and mono allyl ether.The acrylate that also has the monoene propylated compound of polyvalent alcohol and amino alcohol in addition.Another kind of linking agent obtains by the reaction of polyalkylene polyamine such as diethylenetriamine and Triethylenetetramine (TETA) methacrylic acid or methacrylic acid.Can consider diacrylate 1 as linking agent, the 4-butanediol ester, dimethacrylate 1, the 4-butanediol ester, diacrylate 1, the 3-butanediol ester, dimethacrylate 1, the 3-butanediol ester, diacrylate glycol ether ester, dimethacrylate glycol ether ester, the dihydroxyphenyl propane-diacrylate of ethoxylation, the dihydroxyphenyl propane-dimethacrylate of ethoxylation, Ethylene glycol dimethacrylate, diacrylate 1,6-hexylene glycol ester, dimethacrylate 1,6-hexylene glycol ester, the dimethacrylate DOPCP, poly-ethylene glycol diacrylate, polydimethyl vinylformic acid glycol ester, the diacrylate triethyleneglycol ester, the dimethacrylate triethyleneglycol ester, diacrylate tripropylene glycol ester, diacrylate Tetraglycol 99 ester, dimethacrylate Tetraglycol 99 ester, five vinylformic acid dipentaerythritol ester, pentaerythritol tetracrylate, pentaerythritol triacrylate, Viscoat 295, trimethylolpropane trimethacrylate, three (2-hydroxyethyl) isocyanato-triacrylate, three (2-hydroxyl) isocyanato-trimethacrylate, the divinyl ester of polycarboxylic acid, the diallyl ester of polycarboxylic acid, terephthalic acid triallyl ester, toxilic acid diallyl ester, fumaric acid diallyl ester, the hexa-methylene bismaleimides, tri trimellitate vinyl ester, hexanodioic acid divinyl ester, succsinic acid diallyl ester, the ethylene glycol bisthioglycolate vinyl ether, cyclopentadiene diacrylate, triallylamine, the tetraallyl ammonium halide, Vinylstyrene, divinyl ether, N, N '-methylene-bisacrylamide, N, N '-methylene-bis Methacrylamide, Ethylene glycol dimethacrylate and Viscoat 295.Wherein preferred cross-linking agents is N, N '-methylene-bisacrylamide, N, N '-methylene-bis Methacrylamide polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate and triallylamine.
Forming polymer body according to the present invention preferably can prepare by emulsion polymerization, and preferably to have mean particle size be 10-5,000nm; Special preferred average particle size is 150-2,000nm.Most preferably mean particle size is 200-1,000nm.
The mensuration of mean particle size is for example undertaken by going out to add up the particle of going up significant quantity according to the transmission electron microscope number of pictures.
In order to prepare, can use all conditioning agent and initiators commonly used in emulsion polymerization according to forming polymer body of the present invention.The latter's example is an inorganic peroxide, organo-peroxide or H
2O
2With and with the mixture of non-essential one or more reductive agents.
According to the present invention, in the dispersion preparation process or can use ion or non-ionic emulsifying agent arbitrarily afterwards.
Although preferably with the form use of aqueous dispersion, the micropartical that can water be filled directly adds in the building material mixture as solid the polymeric microsphere that water is filled with having no problem within the scope of the present invention according to the present invention.For this reason, micropartical for example (according to method known to those skilled in the art) condense and from aqueous dispersion, separate by method commonly used (for example filter, centrifugal, sedimentation and decantation).The material that obtains can be washed and subsequent drying.
The preferable amount that the forming polymer body joins in the building material mixture is 0.01-5 volume %, especially 0.1-0.5 volume %.At this, the building material mixture form of concrete or mortar (for example with) can contain binding agent such as cement, lime, gypsum or the dehydrated gyp-of hydraulicity commonly used.
Claims (11)
1. the purposes of polymeric microsphere in the building material mixture of hydraulicity is characterized in that, this polymeric microsphere is made of with single level or multi-level mode ethylenically unsaturated monomer.
2. according to the purposes of the polymeric microsphere of claim 1, it is characterized in that ethylenically unsaturated monomer is preferably by vinylbenzene, divinyl, Vinyl toluene, ethene, propylene, vinyl-acetic ester, vinylchlorid, vinylidene chloride, vinyl cyanide, acrylamide, Methacrylamide, the C1-C18-alkyl ester of acrylic or methacrylic acid or their mixture are formed.
3. according to the purposes of the polymeric microsphere of claim 1, it is characterized in that polymeric microsphere also contains linking agent.
4. according to the purposes of the polymeric microsphere of claim 3, it is characterized in that, linking agent is preferably by two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid propylene glycol ester, (methyl) vinylformic acid allyl ester, Vinylstyrene, toxilic acid diallyl ester, trimethylolpropane trimethacrylate, the glycerine dimethacrylate, the glycerine trimethacrylate, tetramethylolmethane tetramethyl-acrylate or their mixture are formed.
5. according to the purposes of the polymeric microsphere of claim 1 or 3, it is characterized in that micropartical uses as the dispersion form.
6. according to the purposes of the polymeric microsphere of claim 1 or 3, it is characterized in that micropartical uses as spray-dired, agglomerative or cryodesiccated powder type.
7. according to the purposes of the polymeric microsphere of claim 1, it is characterized in that the mean particle size that micropartical has is 10-5000nm.
8. according to the purposes of the polymeric microsphere of claim 1, it is characterized in that atomic consumption is 0.01-5 volume %, based on the building material mixture meter.
9. according to the purposes of the polymeric microsphere of claim 1, it is characterized in that atomic consumption is 0.1-0.5 volume %, based on the building material mixture meter.
10. according to the purposes of the polymeric microsphere of claim 1, it is characterized in that building material mixture is made up of the binding agent that is selected from cement, lime, gypsum and dehydrated gyp-.
11. the purposes according to the polymeric microsphere of claim 1 is characterized in that building material mixture is concrete or mortar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006009840.4 | 2006-03-01 | ||
| DE102006009840A DE102006009840A1 (en) | 2006-03-01 | 2006-03-01 | Additive building material mixtures with micro full particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101028972A true CN101028972A (en) | 2007-09-05 |
Family
ID=37872328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610081746.5A Pending CN101028972A (en) | 2006-03-01 | 2006-05-10 | Building material mixture additive containing solid microparticle |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20070204544A1 (en) |
| CN (1) | CN101028972A (en) |
| DE (1) | DE102006009840A1 (en) |
| WO (1) | WO2007099009A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558370A (en) * | 2015-01-22 | 2015-04-29 | 武汉大学 | Application of modified water-absorbing resin as concrete antifreezing reinforcing material |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002068557A1 (en) * | 2001-02-07 | 2002-09-06 | Röhm GmbH & Co. KG | Hot sealing compound for aluminum foils applied to polypropylene and polystyrene |
| DE10350786A1 (en) * | 2003-10-29 | 2005-06-02 | Röhm GmbH & Co. KG | Mixtures for the production of reactive hot melt adhesives and reactive hot melt adhesives obtainable therefrom |
| EP1547985A1 (en) * | 2003-12-23 | 2005-06-29 | Sika Technology AG | Dry admixture for hydraulic binders |
| DE102004035937A1 (en) * | 2004-07-23 | 2006-02-16 | Röhm GmbH & Co. KG | Plastisols with reduced water absorption |
| DE102005042389A1 (en) * | 2005-06-17 | 2006-12-28 | Röhm Gmbh | Heat sealing compound for aluminum and polyethylene terephthalate films against polypropylene-polyvinyl chloride and polystyrene containers |
| DE102005045458A1 (en) * | 2005-09-22 | 2007-03-29 | Röhm Gmbh | Process for the preparation of (meth) acrylate-based ABA triblock copolymers |
| DE102005052130A1 (en) * | 2005-10-28 | 2007-05-03 | Röhm Gmbh | Sprayable acoustics |
| RU2550775C1 (en) * | 2013-12-30 | 2015-05-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" (ФГБОУ ВПО "ИГХТУ") | Complex additive for concrete mixtures |
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| US288657A (en) * | 1883-11-20 | Eeedeeick ntshwitz | ||
| US288665A (en) * | 1883-11-20 | benchard | ||
| US288650A (en) * | 1883-11-20 | Purse-block for seines | ||
| US288653A (en) * | 1883-11-20 | Sandal | ||
| US288658A (en) * | 1883-11-20 | nisewitz | ||
| US288659A (en) * | 1883-11-20 | John c | ||
| US288652A (en) * | 1883-11-20 | Railway-frog | ||
| US288655A (en) * | 1883-11-20 | Jambs mtjiehead | ||
| US288651A (en) * | 1883-11-20 | Michael millbe | ||
| US288654A (en) * | 1883-11-20 | Folding basket | ||
| US288648A (en) * | 1883-11-20 | marshall | ||
| US288656A (en) * | 1883-11-20 | Hiram b | ||
| SE418736B (en) * | 1976-12-23 | 1981-06-22 | Bofors Ab | WHEN IN THE MANUFACTURE OF A CEMENT USE, INCLUDING CEMENT, SAND AND THE WATER INITIATE A RECOVERY OF DISTRIBUTED AIR IN USE |
| US5403894A (en) * | 1991-07-11 | 1995-04-04 | Rohm And Haas Company | A redispersible core-shell polymer powder |
| US5328952A (en) * | 1992-02-14 | 1994-07-12 | Rohm And Haas Company | Multi-stage polymer latex cement modifier and process of making |
| EP0654454A1 (en) * | 1993-11-22 | 1995-05-24 | Rohm And Haas Company | A core-shell polymer powder |
| DE19733157A1 (en) * | 1997-07-31 | 1999-02-04 | Wacker Chemie Gmbh | Crosslinkable powder composition redispersible in water |
| DE19833062A1 (en) * | 1998-07-22 | 2000-02-03 | Elotex Ag Sempach Station | Redispersible powder and its aqueous dispersion, process for its preparation and use |
| JP2000053711A (en) * | 1998-08-11 | 2000-02-22 | Clariant Polymer Kk | Re-dispersible emulsion powder and its production |
| JP2000178055A (en) * | 1998-12-17 | 2000-06-27 | Mitsubishi Rayon Co Ltd | Cement admixture and its production |
| JP2001253742A (en) * | 2000-03-10 | 2001-09-18 | Lion Corp | Freezing and thawing resistance improver for hydraulic inorganic hardened body |
| CA2348149A1 (en) * | 2000-05-25 | 2001-11-25 | The Nippon Synthetic Chemical Industry Co., Ltd. | Redispersible synthetic resin powder and use thereof |
| US6620487B1 (en) * | 2000-11-21 | 2003-09-16 | United States Gypsum Company | Structural sheathing panels |
| DE102005046681A1 (en) * | 2005-09-29 | 2007-04-05 | Construction Research & Technology Gmbh | Use of polymeric microparticles in building material mixtures |
-
2006
- 2006-03-01 DE DE102006009840A patent/DE102006009840A1/en not_active Withdrawn
- 2006-03-24 US US11/388,046 patent/US20070204544A1/en not_active Abandoned
- 2006-05-10 CN CN200610081746.5A patent/CN101028972A/en active Pending
-
2007
- 2007-01-30 WO PCT/EP2007/050908 patent/WO2007099009A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558370A (en) * | 2015-01-22 | 2015-04-29 | 武汉大学 | Application of modified water-absorbing resin as concrete antifreezing reinforcing material |
| CN104558370B (en) * | 2015-01-22 | 2015-12-30 | 武汉大学 | Modified water absorbent resin is as the purposes of concrete antifreezing strongthener |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070204544A1 (en) | 2007-09-06 |
| WO2007099009A1 (en) | 2007-09-07 |
| DE102006009840A1 (en) | 2007-09-06 |
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