WO2021152169A1 - Additif de composition cimentaire pour application machine - Google Patents

Additif de composition cimentaire pour application machine Download PDF

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Publication number
WO2021152169A1
WO2021152169A1 PCT/EP2021/052280 EP2021052280W WO2021152169A1 WO 2021152169 A1 WO2021152169 A1 WO 2021152169A1 EP 2021052280 W EP2021052280 W EP 2021052280W WO 2021152169 A1 WO2021152169 A1 WO 2021152169A1
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WO
WIPO (PCT)
Prior art keywords
cementitious composition
acrylate copolymer
styrene butadiene
cementitious
composition
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PCT/EP2021/052280
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English (en)
Inventor
Thomas Aberle
Lukas Huwiler
Alexander Zapf
Original Assignee
Celanese Switzerland Ag
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Publication of WO2021152169A1 publication Critical patent/WO2021152169A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • 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
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
    • 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
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to an anionic butadiene styrene acrylate copolymer additive that improves the applicability of a cementitious composition by machines and robots.
  • machine-based meaning techniques performed primarily or entirely by machines.
  • machines deposit cementitious compositions (such as mortar, cement, concrete, etc.) in a rapid, controlled and accurate manner.
  • cementitious compositions such as mortar, cement, concrete, etc.
  • These techniques may also be extended into fields other than civil construction, where rapid and accurate deposition of cementitious compositions is desirable (e.g. in mass production items, such as garden pots).
  • Machine-based techniques include applications by (i) semi-manual machines and (ii) robots, such as:
  • 3D Printing also called “additive manufacturing”, which are methods that use robots to apply materials to generate 3D objects. These include extrusion processes, where the material passes an extruder head, which is moved under computer control for a layer-wise deposition of the material;
  • machine application(s) is provided herein as a generic term for all machine-based precision applications of cementitious compositions that use machines (including robots) that are specifically configured to deposit cementitious compositions in a precise, rapid and controlled manner.
  • machine applications falling within this definition are provided above, and include (but are not limited to) shotcrete, machine applied renders, and digital fabrication technologies, such as 3D printing and smart dynamic casting.
  • machine application as used in the following description and claims is therefore to be interpreted in accordance with this specific definition.
  • the term “machine application” is not to be construed as meaning any application by any machine/apparatus (for example, a standard concrete mixer and/or standard concrete mixer chute is not a “machine application” within the context of the present invention).
  • Mortar and concrete applications by machines or robots lack the application skills of a trained worker.
  • the material properties of “3D mortars” i.e. concretes or mortars designed for application by machines or robots by, e.g., extrusion or shaping
  • cementitious composition includes, but is not limited to, concretes and mortars.
  • Conscrete is the most common cementitious composition. However, when the coarsest grain is smaller than 4 mm (in special cases smaller than 16 mm) the material is referred to as “mortar”.
  • cementitious compositions A major challenge with machine applications of cementitious compositions is the immediate succession of contrasting rheology regimes along, e.g., an extruder process line. Mixing, pumping and extrusion are regimes with high to very high shear rates. As such, the cementitious composition must not thicken and stick to the pipelines (which can cause clogging) and must not heat up significantly due to compaction in the pump and extruder head. This can be achieved by cementitious compositions having good shear thinning and anti-sticking properties, as this causes the cementitious compositions to have improved flow and lower adhesion to the internal walls under high shear forces.
  • the flow rate of the cementitious composition must drop rapidly to maintain the shape of the structure being fabricated (i.e. the yield stress must be high so that a first layer of the deposited cementitious composition does not collapse under the load of a subsequent layer).
  • the compressive strength of the cementitious composition must also develop sufficiently quickly to be able to support subsequently printed layers.
  • the machine application applicable cementitious composition must have good wettability of the dry mix, and no crust or skin should form on the surface of the mortar before the next layer of mortar is placed on top, as that can reduce adhesion to subsequently deposited layers (forming what are known in the field as “cold joints”).
  • Additives are often used to impart the required characteristics to mortars and cements.
  • WO 95/28368 and WO 2018/130913 disclose the addition of additives immediately prior to the time when fluidity change is required
  • EP3260258 describes rheology control of a 3D printing mortar by adding a rheology-modifying agent prior to the placement of the mortar in order to increase its yield-stress, typically at a point just before or in the extruder head.
  • WO 95/28368, WO 2018/130913 and EP3260258 deal with active modification of the mortar’s rheology after the initial mixing of the mortar, but just prior to its placement.
  • CN108675671 relates to a thixotropic agent for 3D printing concrete, which is prepared from inorganic flocculant (e.g. magnesium nitrate, iron nitrate, magnesium sulfate or iron sulfate), an organic polymer thixotropic early strength agent (e.g. polyacrylamide), and a foam stabilizer (e.g. calcium lignosulfate, a higher fatty alcohol derivative or alkylphenol ethylene oxide).
  • inorganic flocculant e.g. magnesium nitrate, iron nitrate, magnesium sulfate or iron sulfate
  • an organic polymer thixotropic early strength agent e.g. polyacrylamide
  • a foam stabilizer e.g. calcium lignosulfate, a higher fatty alcohol derivative or alkylphenol ethylene oxide
  • the present invention provides a method for improving the machine application applicability of a cementitious composition (i.e. improve the properties of the cementitious composition such that it is very successfully applied by machine applications). After preparation of the cementitious composition as per the present invention, no further modifications are required for successful use of the composition in machine applications. Accordingly, the present invention allows for fully automated construction processes using digital fabrication technologies.
  • Unmodified cementitious compositions are generally incompatible with machine applications (at least from a practical viewpoint - they do not possess the rheological and setting properties that are necessary for successful application in machine applications, such as 3D printing). As set out above, there are known additives that solve some of these issues, but which simultaneously give rise to other problems.
  • the present invention relates to a method for improving the machine application applicability of a cementitious composition (i.e. improving the applicability of the cementitious composition in machine applications by improving its machine application properties; see below definition of “machine application properties”), comprising adding an anionic styrene butadiene acrylate copolymer to the cementitious composition before the cementitious composition is subjected to machine application processing conditions.
  • the anionic styrene butadiene acrylate copolymer additive improves the machinery compatibility of the cementitious composition (improves the rheological properties of the cementitious composition, thereby avoiding overheating and sticking within the machinery) whilst simultaneously improving the setting properties of the cementitious composition by overcoming the known issues that occur after deposition of the cementitious composition (such as poor yield stress, cold joint formation, etc.). It has been found that a cementitious composition comprising the anionic styrene butadiene acrylate copolymer additive is surprisingly compatible with digital fabrication technologies, particularly 3D printing.
  • the method of the first aspect of the present invention improves the digital fabrication applicability of a cementitious composition (i.e. improves the applicability of the cementitious composition in digital fabrication technologies), and in particular improves the 3D printability of a cementitious composition.
  • machine application properties means the properties that are required for machine application of a cementitious composition, such as the properties required for use in digital fabrication technologies, such as 3D printing.
  • machine application processing conditions means the immediate succession of contrasting rheology regimes that are experienced by cementitious compositions in machine application apparatuses, such as mixing, pumping and/or extrusion regimes with high to very high shear rates.
  • the anionic styrene butadiene acrylate copolymer is added to the cementitious composition before the cementitious composition is subjected to machine application processing conditions to impart, i.a., the shear thinning and anti-sticking properties that are required of the cementitious composition under machine application processing conditions (i.e. when in the machine application apparatus).
  • the cementitious composition preferably comprises the anionic styrene butadiene acrylate copolymer in an amount of from 0,005 to 10 wt.%.
  • the number average molecular weight of the anionic styrene butadiene acrylate copolymer is greater than 5,000, preferably greater than 10,000.
  • the number average molecular weight of the anionic styrene butadiene acrylate copolymer is less than 1 ,000,000, preferably less than 500,000, more preferably less than 250,000, more preferably less than 150,000, and most preferably less than 100,000.
  • the anionic styrene butadiene acrylate copolymer preferably has a glass transition temperature Tg of 50°C to 130°C, preferably 70°C to 100°C, preferably 80°C to 90°C.
  • the anionic styrene butadiene acrylate copolymer preferably has a density of from 950- 1200 kg/m 3 , preferably 1000-1100 kg/m 3 , and preferably about 1 ,050 kg/m 3 .
  • the cementitious composition may comprise one or more inorganic binders selected from hydraulically setting binders, latent hydraulic binders, pozzolanic binders, non- hydraulic binders, or mixtures thereof.
  • the cementitious composition may comprise one or more fillers selected from quartz sand, marble sand, calcium carbonate, limestone, dolomite, basalt, perlite, vermiculite, clay, lime hydrate, silica sand, chalk, talc, mica, fumed silica, polystyrene granules, rubber granules, and mixtures thereof.
  • the cementitious composition may comprise one or more superplasticizers.
  • the cementitious composition is a 3D printable mortar.
  • the anionic styrene butadiene acrylate copolymer is added to a dry cementitious premix composition (e.g. mortar mix, cement mix), thereby forming a “ready to use” dry cementitious premix composition (i.e. a dry cementitious premix composition that forms the improved cementitious composition of the present disclosure upon addition of water).
  • dry cementitious premix means a substantially anhydrous cementitious composition to which no water has been deliberately added.
  • raw materials generally are not completely free of water (e.g. water of crystallisation), and such products can absorb a certain amount of moisture from the atmosphere.
  • the substantially anhydrous cementitious compositions as contemplated herein therefore inevitably contain water in a small quantity.
  • the “dry cementitious premix” of the present disclosure therefore contains less than 10 wt%, preferably less than 5 wt%, more preferably less than 3 wt%, and most preferably less than 1 wt% water, relative to the total weight of the dry cementitious premix composition.
  • the present invention relates to a dry cementitious premix composition for use in machine applications comprising at least one hydraulically setting binder, at least one Pozzolanic binder, at least one superplasticizer, at least one filler, and at least one anionic styrene butadiene acrylate copolymer.
  • a dry cementitious premix composition for use in machine applications comprising at least one hydraulically setting binder, at least one Pozzolanic binder, at least one superplasticizer, at least one filler, and at least one anionic styrene butadiene acrylate copolymer.
  • Such cementitious compositions have been found to be particularly suitable for use in machine applications, notably 3D printing.
  • the present invention relates to a method for improving the machine application of a cementitious composition, comprising preparing a cementitious composition comprising an anionic styrene butadiene acrylate copolymer, feeding the cementitious composition to a machine application apparatus, and then depositing the cementitious composition by machine application (as defined above).
  • the cementitious composition comprising the anionic styrene butadiene acrylate copolymer is prepared by: a) adding the anionic styrene butadiene acrylate copolymer to a dry cementitious premix composition, and then b) mixing the composition of step a) with water to form the prepared cementitious composition.
  • the dry cementitious premix composition comprising the anionic styrene butadiene acrylate copolymer can be prepared offsite in a controlled and accurate manner, which improves formulation accuracy and removes the need for onsite weighing/metering/blending/etc. of additives (which can be, among other things, time consuming, cumbersome, complicated and a cause of errors/variance).
  • a “ready to use” mortar/cement premix can be provided from which the cementitious composition can be very quickly, accurately and easily prepared and then used successfully in a machine application process.
  • cementitious compositions prepared in accordance with the present disclosure do not require any modification during the machine application of the cementitious composition.
  • the prepared cementitious composition fed to the machine application apparatus e.g. 3D printer
  • the machine application apparatus is compositionally substantially the same as the deposited cementitious composition. This removes the need for specialist equipment and operating conditions for feeding additives to the cementitious composition at a downstream stage of the machine application process.
  • the machine application process can be fully automated, as no manual (i.e. human) intervention would be required after the feeding of the raw material (cementitious composition) to the machine application apparatus.
  • the present invention relates to a method for improving the production of a digitally fabricated structure, comprising preparing a cementitious composition comprising an anionic styrene butadiene acrylate copolymer, feeding the prepared cementitious composition to a digital fabrication apparatus, and digitally fabricating a structure using said prepared cementitious composition.
  • the cementitious composition comprising the anionic styrene butadiene acrylate copolymer is prepared by: a) adding the anionic styrene butadiene acrylate copolymer to a dry cementitious premix composition, and then b) mixing the composition of step a) with water to form the prepared cementitious composition.
  • the method comprises 3D printing the structure using said prepared cementitious composition.
  • the present invention relates to a digitally fabricated structure formed from a cementitious composition comprising an anionic styrene butadiene acrylate copolymer.
  • the digitally fabricated structure is preferably a 3D printed structure.
  • the anionic styrene butadiene acrylate copolymer additive significantly improves the machine application applicability of the cementitious composition (i.e. the anionic butadiene styrene acrylate copolymer imparts the necessary thixotropic/rheological and setting properties to the composition that allows for highly successful application of the composition in machine applications, such as digital fabrication technologies).
  • This is a substantial improvement upon previous mortars for machine application, such as those of EP3260258, as the prepared mortar can be used in machine applications without requiring any further modification throughout the digital fabrication process/system.
  • the additive significantly improves the 3D printability of the cementitious composition (i.e. the additive makes the cementitious composition particularly suitable for 3D printing applications by imparting the above described properties to the cementitious composition).
  • 3D printability of a cementitious composition means the ability of the cementitious composition to be used in a successful manner in 3D printing.
  • the anionic styrene butadiene acrylate copolymer for use in the cementitious compositions of the present invention is, as indicated by the polymer nomenclature, a copolymer primarily or entirely formed from at least one substituted or unsubstituted styrene monomeric unit, at least one substituted or unsubstituted butadiene monomeric unit, and at least one substituted or unsubstituted (meth)acrylate monomeric unit, with the proviso that the formed polymer must have an overall negative charge and/or must be capable of readily generating an overall negative charge (preferably under basic conditions).
  • the monomer composition of the anionic styrene butadiene acrylate copolymers that are suitable for use in the present invention is not particularly limited.
  • the at least one substituted or unsubstituted styrene monomeric unit is styrene.
  • the at least one substituted or unsubstituted butadiene monomeric unit is butadiene (1 ,3-butadiene) or C1-C10 alkyl derivatives thereof, such as isoprene (2-methyl-1 ,3-butadiene). Butadiene is most preferred.
  • the at least one substituted or unsubstituted (meth)acrylate monomeric unit is a mixture of (meth)acrylate esters and (meth)acrylic acid, or is (meth)acrylic acid only.
  • Preferred (meth)acrylate esters are substituted or unsubstituted, linear or branched C1-C10 alkyl (meth)acrylates, more preferably substituted or unsubstituted, linear or branched C1-C6 alkyl (meth)acrylates.
  • the anionic charge is formed on the polymer by deprotonating the carboxylic acid moiety of the (meth)acrylic acid monomer units of the polymer under basic conditions, preferably at a pH >9.
  • the anionic styrene butadiene acrylate copolymer may therefore be in the form of a carboxylate salt with a suitable counterion, such as a group 1 or 2 metal ion (e.g. Na + , K + , Ca 2+ , etc.), ammonium, alkyl ammonium, etc.
  • styrene component(s) As used herein, the terms “styrene component(s)”, “butadiene component(s)”, “(meth)acrylates component(s)”, etc. refer to the respective monomeric units after polymerization (i.e. after formation of the polymer).
  • a preferred anionic styrene butadiene acrylate copolymer of the present invention that is formed from styrene monomer, butadiene monomer and acrylic acid monomer is a copolymer that consists of styrene, butadiene and acrylic acid components.
  • the styrene butadiene acrylate copolymer may comprise from about 10 to about 90 parts by weight of the styrene component(s), or from about 20 to about 80 parts by weight of the styrene component(s), or from about 30 to about 70 parts by weight of the styrene component(s), or from about 40 to about 60 parts by weight of the styrene component(s).
  • the anionic styrene butadiene acrylate copolymer may comprise from about 10 to about 90 parts by weight of the butadiene component(s), or from about 20 to about 80 parts by weight of the butadiene component(s), or from about 30 to about 70 parts by weight of the butadiene component(s), or from about 40 to about 60 parts by weight of the butadiene component(s).
  • the anionic styrene butadiene acrylate copolymer generally comprises from about 1 to about 30 parts by weight of (meth)acrylate component(s), from about 5 to about 25 parts by weight of the (meth)acrylate component(s), or from about 10 to about 20 parts by weight of the (meth)acrylate component(s), or up to about 15 parts by weight of the (meth)acrylate component(s).
  • the anionic styrene butadiene acrylate copolymer comprises or consists of from about 10 to about 90 parts by weight of the styrene component(s), from about 10 to about 90 parts by weight of the butadiene component(s), and up to about 30 parts by weight of the (meth)acrylate component(s), or from about 20 to about 80 parts by weight of the styrene component(s), from about 20 to about 80 parts by weight of the butadiene component(s), and up to about 20 parts by weight of the (meth)acrylate component(s), or from about 50 to about 75 parts by weight of the styrene component(s), from about 25 to about 50 parts by weight of the butadiene component(s) and up to about 15 parts by weight of the (meth)acrylate component(s).
  • the (meth)acrylate component(s) may comprise or consist of up to 30 parts by weight of (meth)acrylic acid, or up to 20 parts by weight of (meth)acrylic acid, or up to 15 parts by weight of (meth)acrylic acid, or up to 10 parts by weight of (meth)acrylic acid, or up to 5 parts by weight of (meth)acrylic acid.
  • the total weight content of the styrene component(s), butadiene component(s) and (meth)acrylate component(s) in the anionic styrene butadiene acrylate copolymer is at least 70 parts by weight, or at least 75 parts by weight, or at least 80 parts by weight, or at least 85 parts by weight, or at least 90 parts by weight, or at least 95 parts by weight.
  • the anionic styrene butadiene acrylate copolymer consists of the styrene, butadiene, and (meth)acrylate components.
  • the anionic styrene butadiene acrylate copolymer comprises or consists of from about 10 to about 90 parts by weight of the styrene component(s), from about 10 to about 90 parts by weight of the butadiene component(s) and up to about 30 parts by weight of the (meth)acrylate component(s).
  • the (meth)acrylate component(s) comprise or consist of (meth)acrylic acid.
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene or isoprene, a substituted or unsubstituted alkyl ester of (meth)acrylic acid (such as substituted or unsubstituted, linear or branched C1-C10, preferably C1-C6, alkyl (meth)acrylate(s), for example methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, etc.), and (meth)acrylic acid (
  • the copolymer is formed from styrene, butadiene, a substituted or unsubstituted alkyl ester of (meth)acrylic acid (e.g. linear or branched C1-C10 alkyl (meth)acrylate, such as those listed above), and (meth)acrylic acid.
  • the copolymer is formed from styrene, butadiene, and (meth)acrylic acid.
  • the copolymer may comprise or consist of from about 10 to about 90 parts by weight of the styrene component, from about 10 to about 90 parts by weight of the butadiene component, and up to about 30 parts by weight of the (meth)acrylate component(s).
  • the copolymer comprises or consists of from about 50 to about 75 parts by weight of the styrene component, from about 25 to about 50 parts by weight of the butadiene component, and up to about 15 parts by weight of the (meth)acrylate component(s).
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene, methacrylic acid esters and/or acrylic acid esters, and methacrylic acid and/or acrylic acid.
  • the copolymer may comprise or consist of from about 10 to about 90 parts by weight of the styrene component, from about 10 to about 90 parts by weight of the butadiene component, and up to about 30 parts by weight of the (meth)acrylate component (inclusive of the ester and/or acid component).
  • the copolymer may comprise or consist of from about 10 to about 90 parts by weight of the styrene component, from about 10 to about 90 parts by weight of the butadiene component, up to about 15 parts by weight of the (meth)acrylate ester component(s), and up to about 15 parts by weight of the (meth)acrylic acid component(s), or from about 20 to about 80 parts by weight of the styrene component, from about 20 to about 80 parts by weight of the butadiene component, up to about 15 parts by weight of the (meth)acrylate ester component(s), and up to about 15 parts by weight of the (meth)acrylic acid component(s), or from about 30 to about 70 parts by weight of the styrene component, from about 30 to about 70 parts by weight of the butadiene component, up to about 15 parts by weight of the (meth)acrylate ester component(s), and up to about 15 parts by weight of the (meth)acrylic acid component(s).
  • the above copolymers may comprise up to about 10 parts by weight of the (meth)acrylate ester component(s), and up to about 10 parts by weight of the (meth)acrylic acid component(s), or from 0 to about 10 parts by weight of the (meth)acrylate ester component(s), and up to about 15 parts by weight of the (meth)acrylic acid component(s), or from about 0 to about 5 parts by weight of the (meth)acrylate ester component(s), and up to about 10 parts by weight of the (meth)acrylic acid component(s), or 0 parts by weight of the (meth)acrylate ester component(s), and up to about 15 parts by weight of the (meth)acrylic acid component(s).
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene, acrylic acid esters (preferably substituted or unsubstituted, linear or branched C1-C10 alkyl acrylates, more preferably linear or branched C1-C10 alkyl acrylates, such as those listed above), and acrylic acid.
  • acrylic acid esters preferably substituted or unsubstituted, linear or branched C1-C10 alkyl acrylates, more preferably linear or branched C1-C10 alkyl acrylates, such as those listed above
  • acrylic acid preferably substituted or unsubstituted, linear or branched C1-C10 alkyl acrylates, more preferably linear or branched C1-C10 alkyl acrylates, such as those listed above
  • the relative weights of each of the polymer components may be as described above.
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene, methacrylic acid esters (preferably substituted or unsubstituted, linear or branched C1-C10 alkyl methacrylates, more preferably linear or branched C1-C10 alkyl methacrylates, such as those listed above), and methacrylic acid.
  • methacrylic acid esters preferably substituted or unsubstituted, linear or branched C1-C10 alkyl methacrylates, more preferably linear or branched C1-C10 alkyl methacrylates, such as those listed above
  • methacrylic acid esters preferably substituted or unsubstituted, linear or branched C1-C10 alkyl methacrylates, more preferably linear or branched C1-C10 alkyl methacrylates, such as those listed above
  • methacrylic acid preferably substituted or unsubstit
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene, methacrylic acid esters (preferably substituted or unsubstituted, linear or branched C1-C10 alkyl methacrylates, more preferably linear or branched C1-C10 alkyl methacrylates, such as those listed above), and acrylic acid.
  • the copolymer consists of said polymer components. The relative weights of each of the polymer components may be as described above.
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene, acrylic acid esters (preferably substituted or unsubstituted, linear or branched C1-C10 alkyl acrylates, more preferably linear or branched C1-C10 alkyl acrylates, such as those listed above), and methacrylic acid.
  • the copolymer consists of said polymer components. The relative weights of each of the polymer components may be as described above.
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene and (meth)acrylic acid.
  • the copolymer consists of said polymer components.
  • the copolymer may comprise or consist of up to 90 parts by weight of the styrene component, up to 90 parts by weight of the butadiene component, and up to 30 parts by weight of the acid component.
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene and acrylic acid.
  • the copolymer consists of said polymer components.
  • the copolymer may comprise or consist of up to 90 parts by weight of the styrene component, up to 90 parts by weight of the butadiene component, and up to 30 parts by weight of the acid component.
  • the anionic styrene butadiene acrylate copolymer is formed from at least styrene, butadiene and methacrylic acid.
  • the copolymer consists of said polymer components.
  • the copolymer may comprise or consist of up to 90 parts by weight of the styrene component, up to 90 parts by weight of the butadiene component and up to 30 parts by weight of the acid component.
  • the anionic styrene butadiene acrylate copolymer is formed from (i.e. consists of) styrene, butadiene, and acrylic acid.
  • the copolymer consists of up to 90 parts by weight of the styrene component, up to 90 parts by weight of the butadiene component, and up to 30 parts by weight of the acid component.
  • the copolymer consists of about 10 to 90 parts by weight of the styrene component, about 10 to 90 parts by weight of the butadiene component, and up to 20 parts by weight of the acid component.
  • the copolymer consists of about 50 to 80 parts by weight of the styrene component, about 20 to 50 parts by weight of the butadiene component, and up to 15 parts by weight of the acid component.
  • the copolymer consists of about 55 to 65 parts by weight of the styrene component, about 25 to 35 parts by weight of the butadiene component, and about 10 to 20 parts by weight of the acid component.
  • the anionic styrene butadiene acrylate copolymer is formed from (i.e. consists of) styrene, butadiene, and methacrylic acid.
  • the copolymer consists of up to 90 parts by weight of the styrene component, up to 90 parts by weight of the butadiene component, and up to 30 parts by weight of the acid component.
  • the copolymer consists of about 10 to 90 parts by weight of the styrene component, about 10 to 90 parts by weight of the butadiene component, and up to 20 parts by weight of the acid component.
  • the copolymer consists of about 50 to 80 parts by weight of the styrene component, about 20 to 50 parts by weight of the butadiene component, and up to 15 parts by weight of the acid component.
  • the copolymer consists of about 55 to 65 parts by weight of the styrene component, about 25 to 35 parts by weight of the butadiene component, and about 10 to 20 parts by weight of the acid component.
  • the anionic styrene butadiene acrylate copolymers formed in the manner described above may further comprise at least one further chain polymerizable monomeric unit, such as substituted or unsubstituted vinyl halides, substituted or unsubstituted vinyl amines, substituted or unsubstituted vinyl amides, substituted or unsubstituted acrylamides, substituted or unsubstituted vinyl alcohols, and/or substituted or unsubstituted vinyl aromatics other than styrene.
  • at least one further chain polymerizable monomeric unit such as substituted or unsubstituted vinyl halides, substituted or unsubstituted vinyl amines, substituted or unsubstituted vinyl amides, substituted or unsubstituted acrylamides, substituted or unsubstituted vinyl alcohols, and/or substituted or unsubstituted vinyl aromatics other than styrene.
  • the anionic styrene butadiene acrylate copolymer may comprise the at least one further chain polymerizable monomeric unit in an amount of up to about 30 parts by weight, or up to 25 parts by weight, or up to 20 parts by weight, or up to 15 parts by weight, or up to 10 parts by weight, or up to 5 parts by weight.
  • the copolymer may be a block copolymer, an alternating copolymer, a graft copolymer, or a random copolymer.
  • Preferred graft copolymers include those having a styrene- butadiene backbone and side chains comprising or consisting of (meth)acrylic acid monomer units.
  • the number average molecular weight of the anionic styrene butadiene acrylate copolymer is greater than 5,000, preferably greater than 10,000.
  • the number average molecular weight of the anionic styrene butadiene acrylate copolymer is less than 1 ,000,000, preferably less than 500,000, more preferably less than 250,000, more preferably less than 150,000, and most preferably less than 100,000.
  • the anionic styrene butadiene acrylate copolymer preferably has a density of from about 950-1200 kg/m 3 , preferably 1000-1100 kg/m 3 , and preferably about 1 ,050 kg/m 3 . Densities are measured under atmospheric conditions at 25°C.
  • the anionic styrene butadiene acrylate copolymer preferably has a glass transition temperature Tg of 50°C to 130°C, preferably 70°C to 100°C, preferably 80°C to 90°C.
  • the glass transition temperature Tg of the polymers can be calculated approximately in advance using the Fox equation (according to Fox T. G., Bull. Am. Phys. Soc. 1 , p. 123 (1956)) where XN stands for the mass fraction (wt %/100) of the respective monomer N, and Tg N is the glass transition temperature, in Kelvin, of the homopolymer of monomer N. Tg values for homopolymers are listed for example in Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol.
  • the glass transition temperature Tg of the co-polymers can further be determined experimentally, for example by means of differential scanning calorimetry (DSC) by determining the Tg (Midpoint) of the co-polymer according to ASTM D3418-82(1988)e1.
  • Anionic styrene butadiene acrylate copolymers that are suitable for use in the present invention are commercially available, such as that going by the trade name “RHEMO 500” (ELOTEX® brand available from Nouryon Chemicals AG).
  • the cementitious composition contemplated herein comprises the anionic styrene butadiene acrylate copolymer in an amount of from 0,005 to 10 wt%, preferably 0,01 to 5 wt%, more preferably 0,05 to 1 wt%, and most preferably 0,1 to 0,5 wt%, based on the total weight of the cementitious composition.
  • the cementitious composition contemplated herein is a 3D printable mortar.
  • the cementitious composition contemplated herein preferably comprises one or more inorganic binders.
  • Inorganic binders are inorganic compounds holding solid particles together in a coherent mass. Suitable inorganic binders include hydraulically setting binders, latent hydraulic binders, pozzolanic binders, non-hydraulic binders, and mixtures thereof.
  • Hydraulically setting binders set in the presence of water and include cements.
  • Suitable examples of hydraulically setting binders include Portland cement (CEM I, EN 197-1), blended Portland cements such as CEM II, CEM III, CEM IV, CEM V (EN 197- 1), aluminate cements such as calcium aluminate cement (CAC), calcium-sulfo aluminate cement (CSA), fly ash, calcium phosphate cement and mixtures thereof.
  • Latent hydraulic binders harden by the addition of an activator, usually lime and water. Suitable examples of latent hydraulic binders include fly ash, silico-calcareous cement and blastfurnace slag.
  • Pozzolanic binders are siliceous or silico-aluminous compounds, or a combination thereof. Pozzolanic binders harden in the presence of dissolved Ca(OH) 2 . Suitable examples of pozzolanic binders include microsilica (also referred to as silica-fume), metakaolin, vitrified calcium alumino-silicate (VCAS), ground recycled glass pozzolans, burnt shale, diatomaceous earth, moler, rice husk ash, air cooled slag, calcium metasilicate, volcanic slag, volcanic tuff, volcanic ash, trass, and mixtures thereof. Non-hydraulic inorganic binders do not harden in the presence of excess water.
  • non-hydraulic inorganic binders include calcium sulfate hemihydrate, anhydrite, quicklime, hydrated lime, magnesia cements, and mixtures thereof.
  • the cementitious compositions contemplated herein may comprise one or more further polymers selected from vinyl-ester co-polymers containing one or more vinyl ester units and one or more monomer units selected from the group consisting of olefins, vinyl aromatics, vinyl halides, acrylic esters, methacrylic esters, monoesters or diesters of fumaric and/or maleic acid, and silicon-containing monomers.
  • Preferred further polymers are those that have a glass transition temperature Tg of -20°C to +30°C, preferably -15°C to +25°C.
  • the amount of the one or more further polymers is preferably in the range of 0,5 to 40 wt%, preferably 0,5 to 25 wt%, based on the total weight of the cementitious composition.
  • Co-polymers within the meaning of the invention include co-polymers comprising two or more different monomers or monomer units.
  • suitable copolymers include bipolymers, ter-polymers, and quaterpolymers.
  • Suitable vinyl ester monomers include vinyl esters of carboxylic acids having 1 to 15 carbon atoms. Preferred are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2- ethylhexanoate, vinyl laurate, 1 -methylvinyl acetate, vinyl pivalate, and vinyl esters of alpha-branched monocarboxylic acids having 9 to 11 carbon atoms, such as vinyl versatate, for example VeoVaTM9, VeoVaTM 10, VeoVaTM 11.
  • Suitable examples of suitable vinyl ester co-polymers include co-polymers comprising one or more vinyl ester units and one or more monomer units selected from olefins, vinylaromatics, vinyl halides, acrylic esters, methacrylic esters, monoesters or diesters of fumaric and/or maleic acid, or silicon-containing monomers.
  • Suitable examples of vinyl ester co-polymers include ethylene (E) vinyl acetate (VA) co-polymers (EVA polymers) and ter-polymers further comprising vinyl chloride (VC) (VA/EA C polymers), or vinyl acetate (VA) versatate (VeoVa) based polymers such as (VA/VeoVa polymers).
  • Suitable monomers from the group of acrylic esters and methacrylic esters include esters of unbranched or branched alcohols having 1 to 15 carbon atoms.
  • Preferred methacrylic esters or acrylic esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n- butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, and 2-ethylhexyl acrylate.
  • Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and 2-ethylhexyl acrylate.
  • Olefin monomers have the general formula C n Pb n .
  • Suitable olefin monomers include ethylene and propylene.
  • Diene monomers are hydrocarbons containing two carbon double bonds.
  • Suitable diene monomers include 1 ,3-butadiene and isoprene.
  • Suitable vinylaromatic monomers inlcude styrene, methylstyrene, and vinyltoluene.
  • Vinyl halide monomers are alkene monomers with at least one halide substituent bonded directly on one of the alkene carbons. Suitable halide substituents are Cl, Br, and/or I. .A preferred vinyl halide is vinyl chloride.
  • vinyl chloride co-polymers include copolymers with olefins, such as ethylene or propylene, and/or vinyl esters, such as vinyl acetate, vinyl laurate, or vinyl esters of a branched carboxylic acid having 9 to 11 carbon atoms, and/or acrylic esters and/or methacrylic esters of alcohols with 1 to 15 carbon atoms, such as methyl acrylate and methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl-acrylate, tert-butyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate and/or monoesters or diesters of fumaric and/or maleic acid, such as the dimethyl, methyl tert-butyl, di-n-butyl, di-n-but
  • Suitable vinyl chloride-ethylene co-polymers further include vinyl chloride-ethylene co polymers containing 60 to 98 wt % of vinyl chloride units and 1 to 40 wt % of ethylene units, the amounts in wt % being based on the total weight of the co-polymer and adding up in each case to 100 wt %.
  • silicon-containing monomers include silanes, polymethylhydrogensiloxanes, siloxane resins, polysilanes, organosilanols, disiloxanes, oligosiloxanes, polysiloxanes, and organosiliconates.
  • Further suitable examples include vinylsilanes and methacryloxysilanes, such as acryloyloxypropyltri(alkoxy)silanes, methacryloyloxypropyltri(alkoxy)silanes, vinyltrialkoxysilanes, and vinylmethyldialkoxysilanes.
  • Suitable examples of co-polymers of one or more vinyl esters further include vinyl acetate, with 1 to 50 wt %, preferably 10 to 30 wt% of ethylene; co-polymers of vinyl acetate with 1 to 50 wt % of one or more further co-monomers from the group of vinyl esters having 1 to 12 carbon atoms in the carboxylic acid radical, such as vinyl propionate, vinyl laurate, vinyl esters of alpha-branched carboxylic acids having 9 to 11 carbon atoms such as VeoVaTM 9, VeoVaTM 10, VeoVaTM 11 , and optionally 1 to 50 wt % of ethylene; co-polymers of one or more vinyl esters, 1 to 50 wt % of ethylene, and preferably 1 to 60 wt % of (meth)acrylic esters of unbranched or branched alcohols having 1 to 15 carbon atoms, more particularly n-butyl acrylate or 2-ethylhexyl
  • Polymers disclosed herein are generally prepared in an aqueous medium and preferably by an emulsion or suspension polymerization process, such as the process described in DE-A 102008043988.
  • Protective colloids and/or emulsifiers may be used during the polymerization.
  • the obtained polymers are in the form of aqueous dispersions and can be converted, as described in DE-A 102008043988, into corresponding redispersible powders, e.g. by spray-drying.
  • a drying aid may be used, in a total amount of 3% to 40% by weight, preferably 5% to 30% by weight, based on the polymeric constituents of the dispersion.
  • Preferred drying aids are polyvinyl alcohols.
  • the polymers disclosed herein may also be spray-dried without requiring the use of a drying aid.
  • the cementitious composition contemplated herein may comprise one or more fillers.
  • suitable fillers include quartz sand, marble sand, calcium carbonate, limestone, dolomite, basalt, perlite, vermiculite, clay, such as expanded or sintered clay, lime hydrate, silica sand, chalk, white lime hydrate, talc, mica, fumed silica, polystyrene granules, rubber granules, and mixtures thereof.
  • the cementitious composition contemplated herein may comprise one or more thickeners.
  • Suitable thickeners include starch, starch ethers, cellulose ethers, guar ethers and welan gums or inorganic thickeners such as clays.
  • Cellulose ethers and the guar ethers are preferred and include alkyl, hydroxyalkyl and/or carboxymethyl ethers.
  • Suitable alkyl groups include methyl, ethyl, propyl and/or C4- to C30- alkyl groups.
  • Suitable hydroxyalkyl groups include hydroxyethyl and/or hydroxypropyl groups.
  • the cellulose ethers or guar ethers have the additional advantage that they can further help to control mortar slurry properties including water demand, workability, open time and water retention during the application of the mortar slurry.
  • the cementitious composition contemplated herein may comprise one or more hydrophobizing additives.
  • Hydrophobizing additives provide protection for the cured mortar against high surface tension fluids, in particular against water.
  • Suitable hydrophobizing additives include organosilicon compounds, such as alkyl- trialkoxysilanes and/or dialkyldialkoxysilanes.
  • suitable alkyl groups include C& to C12 alkyl groups.
  • suitable alkoxy groups include methoxy, ethoxy, propoxy and/or a butoxy group.
  • Further suitable hydrophobizing additives can be selected from fatty acids, fatty acid salts, and fatty acid derivatives.
  • the cementitious composition contemplated herein may comprise one or more superplasticizers.
  • Superplasticizers SP's
  • Suitable superplasticizers include naphthalene and/or naphthalene-based superplasticizers, melamine and/or melamine-based superplasticizers, lignosulfonates, and polycarboxylic acids.
  • a particularly preferred cementitious composition that has been found to be particularly suitable for use in machine application, such as 3D printing, comprises at least one hydraulically setting binder, at least one Pozzolanic binder, at least one superplasticizer, at least one filler, and an anionic styrene butadiene acrylate copolymer.
  • Such cementitious compositions are advantageously provided in dry premix form as “ready to use” cementitious compositions that require only the addition of water before use. The benefits of such dry premix compositions are set out above.
  • cementitious compositions contemplated herein may also comprise further standard cement/mortar additives known in the art, such as biocides, pigments, defoaming agents, etc. Such additives are well known to the skilled person.
  • compositions of the present invention are a substantial improvement upon previous cementitious compositions for use in machine application, as the rheology modifying additive (anionic styrene butadiene acrylate copolymer) can be added to the composition before it is introduced into the machine application system and no further modification of the mortar is needed thereafter.
  • the rheology modifying additive anionic styrene butadiene acrylate copolymer
  • the composition can be used directly in digital fabrication technologies without requiring any further manipulation during the printing process/apparatus.
  • Machine application can be defined as the application of digital modeling and technologies to the production of custom material objects.
  • Such technologies are well known in the art; see, for example, Wangler et al. (RILEM Tech. Lett. Vol 1 , 2016, available from https://letters.rilem.net/index.php/rilem/article/view/16), which provides a review of several methods of digital fabrication with concrete.
  • any type of cementitious composition such as mortar may be modified for machine application, such as mortars for decorative objects (e.g., plant pot), decorative building elements (e.g., plasters), precast concrete elements (e.g., columns or beams) or structural building elements (e.g., concrete wall). Therefore, such mortars may be based on a large variety of different mortar types.
  • the mortar should have excellent wetting properties, however changes in water demand due to the presence of any additives can have a detrimental effect upon the flowability properties of the mortar.
  • the wetted mortar must be able to flow freely (i.e.
  • the dry mortar compositions of Tables 1 and 2 were mixed with water using a Hobart mixer. After mixing, the fresh mortar was allowed to rest. The viscosity of the rested fresh mortar was evaluated (fluid/low viscous, plastic, thickened/high viscous), and the shear thickening or thinning behavior of the fresh mortar was determined (re-stirring by hand). The water demand and observed physical changes are set out in Table 3.
  • the buildability of the mortars i.e. ability of the mortar to form stable layers upon which further mortar layers can be built upon was tested by extruding 10 layers on top of each other within one minute. Additional factors taken into consideration for determining the buildability of the extruded and deposited mortar layer were homogeneity (no segregation into cake and serum), smoothness (no bubbles, holes or cracks), and cold joint formation.
  • mortar layer behaves too much like a liquid under stress, even when water content is reduced
  • the yield strength is the minimum strength required to deform a material and initiate flow. It can be measured as a function of time to follow the evolution of strength build up.
  • early stiffening and setting would cement the probe of the rheometer and destroy the device. Therefore, non-mechanical methods, such as ultrasonic (US) velocity measurement deliver information about the elasticity of the material, which refers to the buildup of a structure.
  • US signal is continuous and delivers information about the stiffening and setting dynamics, which refer to yield and early strength. Any retardation of early strength development can be detected by shift of the curves to later times.
  • integrated thermo-couples allow to measure the samples temperature over time. Usually, setting is an exothermal reaction.
  • any retardation can independently be detected by a shift of the temperature signal to later times, as well.
  • the initial US velocity value and the US velocity 10 min after mixing give an indication of the early yield strength development. Retardation was determined by delay of exothermal signal (rise of temperature; measured by thermocouple). Table 5.
  • the RHEMO 500 additive showed acceptable evolution of yield and acceptable setting times.
  • the compressive and flexural strength of the mortars was tested according to EN 1015-11 after 24 hours. This data is important because it reveals if the material is weakened either by (i) high air content, (ii) high capillarity, due to high water demand, (iii) retardation of setting, which results in low degree of early hydration, or (iv) early crack formation, due to segregation or drying.
  • the RHEMO 500 additive showed good 1-day strength.
  • the Floset 130M additive did not provide acceptable compressive and flexural strength after 24 hours.

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Abstract

La présente invention concerne un procédé pour améliorer les propriétés d'application machine d'une composition cimentaire, comprenant l'ajout d'un copolymère d'acrylate de butadiène-styrène anionique à la composition cimentaire avant que la composition cimentaire soit soumise à des conditions de traitement d'application machine.
PCT/EP2021/052280 2020-02-01 2021-02-01 Additif de composition cimentaire pour application machine WO2021152169A1 (fr)

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