EP4532441A1 - Composition for waterproofing membranes - Google Patents
Composition for waterproofing membranesInfo
- Publication number
- EP4532441A1 EP4532441A1 EP23729401.2A EP23729401A EP4532441A1 EP 4532441 A1 EP4532441 A1 EP 4532441A1 EP 23729401 A EP23729401 A EP 23729401A EP 4532441 A1 EP4532441 A1 EP 4532441A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- composition
- powdery
- component
- monomers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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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
- C04B28/04—Portland cements
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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
- C04B2103/0065—Polymers characterised by their glass transition temperature (Tg)
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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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
- C04B2111/00801—Membranes; Diaphragms
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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
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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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
- C04B2111/34—Non-shrinking or non-cracking materials
Definitions
- the present invention relates to compositions for producing waterproofing membranes comprising a pozzolanic material, at least one powdery filler and an organic polymer P having a glass transition temperature of at most +15°C either in form of an aqueous polymer dispersion or of a polymer powder obtained from the aqueous polymer dispersion.
- calcium aluminate cement in particular a high alumina cement (HAC), calcium sulfonaluminate cement (CSA) and combinations thereof with OPC have been suggested as mineral binders.
- these systems often require a lithium based accelerator, such as lithium carbonate, which is expensive and of limited availability due to high demand for electromobility.
- composition of the invention is not necessarily a physical mixture of components A, B, C and D and optionally further components disclosed herein, but can constitute any desired combination of sub-compositions or of components thereof in which they are not necessarily formulated together.
- a composition is a two-com- ponent kit comprising a first composition (I) which comprises the components A, B and C and a second composition (II) which comprises the component D.
- This composition form is for example expedient when a component of one of the compositions interferes with one or more of the components of the other composition. For instance, if composition (II) is aqueous, the water contained therein may start the reaction of components A and B, which is of course to be prevented until the composition is put into application at the desired point of time.
- the first composition may principally also be formulated as a kit of parts, but is preferably formulated as a physical mixture. It is also possible to formulate the composition of the present invention as a 1 K formulation comprising the polymer P in the form of a polymer powder. Moreover, it is possible to formulate the components A and B as a first powdery composition and to add the components C and D and optionally water immediately before the composition is used for providing the aqueous slurry forming the water-proofing membrane.
- pozzolanic material refers to natural and artificial pozzolans.
- Pozzolans are natural or artificial siliceous or siliceous and aluminous rock materials and have been used as construction material since antiquity, e.g. as alphabet caementitium in ancient Rome. They are generally formed of silicium dioxide, clay, limestone, iron oxide and alkaline substances under heat. In themselves, they possess little or no value as binders, but, in finely divided form and in the presence of water, react chemically with calcium hydroxide at ordinary temperature to form a material possessing cementitious properties.
- Natural pozzolans are either magmatic rock, like volcanic tuff or volcanic trass, or sedimentary rock containing a substantial amount of soluble silicic acid and partially also aluminium oxide (clay).
- Other pozzolan sources originate from rock metamorphosis caused by meteor strike, like Bavarian trass, Ries trass or Suevit. Trass can thus be of volcanic origin or originate from meteor impact.
- volcanic trass is poz- zolanic volcanic tuff originating from a volcanic eruption of the Laacher See volcano in the Eifel, Germany and occurring in the Brohl and the Nette valleys.
- “volcanic trass” relates however to any pozzolanic volcanic tuff, irrespective of its origin.
- Artificial pozzolans are for example brick powder or fly ash as obtained, for example, from brown coal- or hard coal-fired power stations, waste slag, such as blast furnace slag and steel furnace slag resulting from the manufacture of iron and steel.
- non-slaked lime refers to calcium oxide (CaO) and may also be called burnt lime or quicklime.
- the term “powdery” with respect to a powdery material means that the material has a particle size of at most 1000 pm, in particular of at most 750 pm.
- “powdery” pozzolanic material means that the pozzolanic material has a particle size of at most 500 pm, in particular of at most 300 pm, preferably of at most 250 pm or of at most 200 pm and specifically at most 100 pm.
- “Powdery” cement means that the cement has a particle size of at most 500 pm, in particular of at most 400 pm, preferably of at most 300 pm or of at most 250 pm and specifically of at most 200 pm.
- “Powdery” non-slaked lime means that the non-slaked lime has a particle size of at most 500 pm, in particular of at most 300 pm, preferably of at most 250 pm or of at most 200 pm and specifically of at most 100 pm.
- the particle size in the filler is not very critical and may be somewhat larger than the particles of the powdery components A and B. It is typically at most 1000 pm, in particular of at most 700 pm.
- the polymer P of component D may be used in the composition as a polymer powder or as an aqueous polymer dispersion. If the polymer P of component D is present in the form of a polymer powder, the particle size of the polymer powder is not very critical, but is such that the polymer powder can be easily dispersed in water. It is often in the range given above for the pozzolanic material and typically has a particle size of at most 300 pm or at most 250 pm or at most 200 pm. Particle sizes and particle size distributions can be determined using a wide variety of measurement methods known per se to the person skilled in the art, for example via sieve analyses according to DIN 66165-2:2016-08, sedimentation or light scattering, e.g. laser diffraction in accordance with DIN ISO 13321 :2004-10. In the present case, given particle sizes of the components of the powdery composition A are either such as indicated by the commercial producer or as determined using sieve analyses according to DIN 66165-2:2016-08.
- the pozzolanic material comprises trass (in powdery form, of course).
- trass preference is given to volcanic trass. More preference is given to volcanic trass.
- the trass, in particular the volcanic trass constitutes at least 15% by weight, in particular at least 20% by weight, preferably at least 25% by weight and especially at least 30% by weight of the total amount of the pozzolanic material of the component A and may constitute up to 100% by weight of the component A.
- the component A is essentially free of non-pozzolanic cements, i. e. the amount of non- pozzolanic cement in the component A is at most 10% by weight, in particular at most 5% by weight, based on the total weight of the component A.
- the pozzolanic material additionally comprises artificial pozzolanic material, such as brick powder or fly ash as obtained, for example, from brown coal- or hard coal-fired power stations.
- the artificial pozzolanic material is preferably brick powder or powdery waste slag.
- the brick powder also called brick dust or clay dust, is preferably a recycled material, obtained e.g. from comminuting brick waste, e.g. discarded building bricks and roof tiles.
- Powdery waste slag is ground waste slag, e.g. ground waste slag, such as ground blast furnace slag and ground steel furnace slag resulting from the manufacture of iron and steel.
- the artificial pozzolanic material not only reduces the amount of natural pozzolanes, thus allowing to preserve pristine natural resources, but also contributes to the flexibility and elasticity and thus crack resistance of the set system.
- the pozzolanic material comprises or consists of i. 15 to 90% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and ii. 10 to 85% by weight, based on the total amount of pozzolanic material, of a powdery artificial pozzolanic material, in particular brick powder, where the total amount of powdery trass and brick powder is preferably at least 90% by weight, in particular at least 95% by weight, based on the total amount of the component A.
- the pozzolanic material comprises or consists of i. 20 to 85% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
- the pozzolanic material comprises or consists of i. 25 to 80% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
- the pozzolanic material comprises or consists of i. 30 to 75% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
- the cement component B is a cement classified as CEM I.
- CEM I a cement of class CEM I, contains at least 95% of Portland cement clinker.
- OPC ordinary Portland cement
- the cement of class CEM I may be any type of OPC, including Portland cement classified as CEM I 52.5 N, CEM I 42.5 N, CEM I 32.5 N, CEM I 52.5 R, CEM I 42.5 R or CEM I 32.5 R.
- component B may be replaced by another hydraulic binder, hereinafter component B’, such as gypsum, calcium sulfoaluminate cements (CSA) and/or calcium aluminate cements (HAC), provided that the amount of Portland cement clinker and its ratio to trass is as given above.
- component B such as gypsum, calcium sulfoaluminate cements (CSA) and/or calcium aluminate cements (HAC), provided that the amount of Portland cement clinker and its ratio to trass is as given above.
- the relative amount of the component B will be at least 60% by weight, in particular at least 75% by weight and may be as high as 100% by weight, based on the overall weight of the components B and B’ in the composition of the invention.
- the component B’ is absent or amounts to less than 5% by weight, based on the overall weight of the components B and B’ in the composition of the invention.
- the weight ratio of the component A to the component B is preferably in the range of 25 : 75 to 95 : 5, in particular in the range of 30 : 70 to 85 : 15 and especially in the range of 40 : 60 to 80 : 20.
- the overall amount of the component A is preferably in the range of 25 to 50 % by weight, in particular in the range of 30 to 45% by weight, based on the total weight of the components A, B optionally B’ and C.
- the composition comprises 10 to 40% by weight, in particular 15 to 30% by weight, based on the total weight of the component A, B and C and optionally B’, of volcanic trass and 10 to 40% by weight, in particular 15 to 30% by weight, based on the total weight of the components A, B and C and optionally B’, of brick powder.
- the overall amount of the components A and B and optionally B’ is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, based on the total weight of the components A, B and C and optionally B’.
- the component C hereinafter also termed filler typically comprises a particulate mineral material, in particular a particulate stone material customarily used as reinforcement material to add strength to the overall composite material.
- the filler as used in the present composition may be any of the usual construction filler, including mineral filler such as rock powder and sand; and recycle filler produced from the recycling of concrete, which is itself chiefly manufactured from mineral filler.
- Mineral fillers such as powdery dolomite, granites, gravel, sandstone, limestone, basalt and the like can also be used as filler.
- the present powdery filler may also organic concrete “filler”, such as rubber or bitumen.
- the present powdery filler typically includes also mixtures of two or more of the above-listed fillers.
- the overall amount of the powdery filler is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, based on the total weight of the components A, B and C and optionally B’.
- the powdery filler comprises sand.
- the powdery filler comprises preferably at least 50% by weight, more preferably at least 60% by weight, and up to 100% by weight, based on the total weight of the component C, of sand.
- the sand is a combination of medium sand and fine sand.
- Fine sand in terms of the present invention is defined in accordance with DIN 4022:1987 and is sand with an equivalent diameter of 0.063-0.2 mm.
- Medium sand in terms of the present invention is defined in accordance with DIN 4022:1987 and is sand with an equivalent diameter of 0.2-0.63 mm.
- Medium sand and fine sand are preferably present in a weight ratio of from 2: 1 to 1 :5, more preferably from 1 :1 to 1 :3, in particular from 1 :1.5 to 1 :3.
- the filler comprises an organic powdery recycling material, such as powdered rubber.
- the powdered rubber is a recycle material obtained, for example from comminuting discarded tires and the like.
- the powdered rubber not only reduces the amount of natural mineral fillers, such as sand, thus allowing to preserve their pristine natural resources, but also contributes to the flexibility and elasticity and thus crack resistance of the set system.
- the organic powdery recycling material has preferably a particle size of at most 500 pm and typically of at least 50 pm.
- the organic powdery recycling material if contained in the composition, is preferably present in an amount of from 5 to 50% by weight, more preferably from 10 to 40% by weight, in particular 10 to 35% by weight, based on the total weight of the component C. Its amount, if present, is typically in the range of 2 to 25% by weight, in particular 5 to 15% by weight, based on the total weight of the components A, B and C and optionally B’.
- the composition may contain other ingredients.
- an additional ingredient is kaolin, hereinafter component E.
- the composition of the invention additionally comprises powdery kaolin.
- Kaolin also known as China clay, is a hydrated aluminum silicate, which can be approximately described by the simplistic and idealized formula AI2O3 ⁇ 2SiC>2 ⁇ 2H2O. It is a natural, fine-grained and well crystallized clay mineral with a layered structure.
- Kaolin if contained in the composition, is preferably present in an amount of from 1 to 10% by weight, more preferably from 1 to 5% by weight, in particular from 2 to 3% by weight, based on the total weight of the components A, B and C and optionally B’.
- the kaolin has preferably a particle size of at most 500 pm, more preferably of at most 300 pm, in particular of at most 100 pm.
- the composition of the invention may also contain non-slaked lime as a component F.
- non-slaked lime as a component F.
- the use of non-slaked lime in the present composition leads to a distinctly faster setting. Moreover, it allows to reduce the amount of calcium needed for setting.
- the amount of the non-slaked lime is preferably in the range of 5 to 20% by weight, in particular in the range of 8 to 15% by weight, based on the total weight of the components A, B and C and optionally B’.
- a particular group of embodiment of the invention relates to compositions which do not contain non-slaked lime or less than 5% by weight of non-slaked lime, based on the total weight of the components A, B and C and optionally B’.
- composition of the invention may moreover contain other additives typical for such formulations, such as rheology modifiers (e.g. thickeners, plasticizers), accelerators or retardants (for the setting process) and wetting agents or dispersants, respectively.
- rheology modifiers e.g. thickeners, plasticizers
- accelerators or retardants for the setting process
- wetting agents or dispersants wetting agents or dispersants, respectively.
- component G The total amount of these additives is usually at most 5% by weight, preferably at most 2% by weight, based on the total weight of components A, B and C and optionally B’ and e. g. in the range of 0.1 to 5 % by weight or in the range of 0.2 to 2% by weight, if present.
- wetting agents and “dispersants” are used synonymously. They allow for reducing the amount of make-up water required for producing the slurry.
- Suitable wetting agents or dispersants are, for example, sodium, potassium or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers, polyphosphonates, such as sodium 1-hydroxyethane-1 ,1 -diphosphonate, and also salts of naphthalenesulfonic acids, more particularly their sodium salts.
- polymeric dispersants such as alkali metal salts and ammonium salts of acrylic acid polymers or maleic anhydride polymers.
- a metal salt of polyacrylic acid is used as a dispersant or wetting agent, respectively.
- the composition of the invention contains the dispersant, in particular the polymeric dispersant, in an amount of from 0.1 to 5% by weight, in particular of from 0.3 to 3% by weight, based on the total weight of the components A and B.
- the composition is formulated as a 2K composition which comprises a first powdery composition (I), which contains the powdery components A, B and C and optionally the powdery components B’, E, F and G, and a second composition (I) which contains the polymer P, in particular in the form of an aqueous polymer dispersion.
- a first powdery composition (I) which contains the powdery components A, B and C and optionally the powdery components B’, E, F and G
- a second composition (I) which contains the polymer P, in particular in the form of an aqueous polymer dispersion.
- composition (I) comprises or consists of:
- component C 35 to 65% by weight of the filler (component C), in particular a combination of sand and an organic powdery recycling material, in particular powdery rubber;
- composition (I) comprises or consists of:
- component A 30 to 45% by weight of the component A, in particular a combination of volcanic trass and brick powder;
- component C 40 to 55% by weight of the filler (component C), in particular a combination of sand and an organic powdery recycling material, in particular powdery rubber;
- a further additive in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B and optionally B’ is preferably in the range of in the range of 45 to 59% by weight, and where the weight ratio of the trass of component A to the cement clinker of the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
- a further additive in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, and where the weight ratio of the trass of component A to the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
- the composition comprises or consists of: (a.1 ) 15 to 30% of trass, in particular volcanic trass;
- a further additive in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B and optionally B’ is preferably in the range of 44 to 60% by weight, and where the weight ratio of the trass of component A to the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
- the composition of the invention further comprises a polymer P.
- the polymer P of the component B may be present either as an aqueous polymer dispersion or as a polymer powder, in particular a polymer powder which is obtained by spray-drying of an aqueous polymer dispersion of the polymer P.
- the polymer P comprises a polymer powder obtained from the above-described aqueous polymer dispersion, where the polymer of the aqueous polymer dispersion has a glass transition temperature Tg of at most +15°C, in particular at most +10°C, more particularly at most +5°C, especially at most 0°C.
- the glass transition temperature Tg is at least -60°C, frequently at least -50°C, in particular at least -40°C more particularly at least -30°C and especially at least -25°C.
- the Tg of the polymer is in the range of -60 to +15°C.
- the polymers P are insoluble in water and are present in the form of discrete polymer particles.
- the average diameter of the polymer particles present in aqueous dispersion is generally in the range from 10 to 1000 nm, frequently in the range from 20 to 850 nm, e.g. from 100 to 700 nm.
- this specification means the Z average particle diameter as determined by dynamic light scattering (also termed quasielastic light scattering) of an aqueous polymer dispersion diluted with deionized water to 0.001 to 0.5% by weight at 22°C by means of a HPPS from Malvern Instruments, England. What is reported is the cumulant Z average diameter calculated from the measured autocorrelation function (ISO Standard 13321 ).
- the aqueous dispersion of the polymer P is generally a polymer obtained by emulsion polymerization of ethylenically unsaturated monomers M, hereinafter also referred to as polymer emulsions.
- Polymer emulsions are familiar to the skilled person and are prepared, for example, in the form of an aqueous polymer dispersion by means of radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers M. This technique has been exhaustively described in the art, and is therefore well known to the skilled person [cf., e.g., Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 to 677, John Wiley & Sons, Inc., 1987; D. C.
- the radically initiated aqueous emulsion polymerization is normally accomplished by dispersing the ethylenically unsaturated monomers in aqueous medium, generally with accompanying use of dispersing assistants, such as emulsifiers and/or protective colloids, and polymerizing them by means of at least one water- soluble radical polymerization initiator.
- dispersing assistants such as emulsifiers and/or protective colloids
- the residual amounts of unreacted ethylenically unsaturated monomers are frequently lowered by chemical and/or physical techniques that are likewise known to the skilled person [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586, and 19847115]; the polymer solids content is adjusted to a desired level by dilution or concentration; or the aqueous polymer dispersion is admixed with further customary adjuvants, such as bactericidal, foam-modifying or viscositymodifying additives, for example.
- further customary adjuvants such as bactericidal, foam-modifying or viscositymodifying additives, for example.
- водородн ⁇ е ⁇ ок ком ⁇ онент ⁇ As well as these so-called primary aqueous polymer dispersions, the skilled person also knows of what are called secondary aqueous polymer dispersions. These are understood to be aqueous polymer dispersions in whose preparation the polymer is generated outside of the aqueous dispersing medium, as for example in solution in a suitable nonaqueous solvent. This solution is subsequently transferred into the aqueous dispersing medium, and the solvent is separated off with dispersing, generally by distillation.
- secondary aqueous polymer dispersions These are understood to be aqueous polymer dispersions in whose preparation the polymer is generated outside of the aqueous dispersing medium, as for example in solution in a suitable nonaqueous solvent. This solution is subsequently transferred into the aqueous dispersing medium, and the solvent is separated off with dispersing, generally by distillation.
- the aqueous polymer dispersion of the polymer P is a primary aqueous polymer dispersion, in particular an aqueous polymer dispersion, which is obtained by aqueous emulsion polymerization of ethylenically unsaturated monomers M.
- the polymer P is a copolymer of ethylenically unsaturated monomers M.
- copolymer refers to polymers which are made of two or more, e.g. 2, 3, 4, 5 or 6 or more different ethylenically unsaturated monomers M.
- the copolymer comprises both ethylenically unsaturated comonomers with a rather low and with a higher solubility in water, where the comonomers of rather low solubility preferably constitute the major part of the polymer.
- Ethylenically unsaturated monomers of low water-solubility are those having a solubility in water of not more than 50 g/l at 20°C and 1 bar.
- monomers M 1 Monomers of higher water-solubility are those having a solubility in water of at least 60 g/l at 20°C and 1 bar. These monomers are hereinafter referred to as monomers M2.
- the polymer P is composed of i) 80 to 99.9 pphm, more particularly 85 to 99.5 pphm, of at least one neutral, nonfunctional monoethylenically monomer M.1 having a water-solubility in deionized water of not more than 50 g/l at 20°C and 1 bar, e. g. in the range of 0.01 to 50 g/l; and ii) 0.1 to 20 pphm, more particularly 0.5 to 15 pphm, of at least one further ethyleni- cally unsaturated monomer other than the monomers M 1 .
- pphm means part per hundred parts of monomers and is an abbreviation of the term “% by weight, based on the total amount of monomers”.
- neutral means that the monomer has neither a basic or acidic group nor a ionic group.
- non-functional means that the monomer has no functional group, which is capable to undergo a polymer analogue reaction, i. e. a bond-forming reaction with another group of the polymer or with a crosslinking agent or with inorganic matter.
- unsaturated monomer other than the monomers M1 refers to monoethylenically unsaturated neutral monomers having a water-solubility in deionized water of more than 50 g/l at 20°C and 1 bar, e. g. at least 60 g/l at 20°C and 1 bar; monoethylenically unsaturated monomers having a basic or acidic group or a ionic group, e. g.
- a keto carbonyl group an aldehyde group, an isocyanate group, a 1 ,3-dicarbonyl group, a urea group, an N- alkylolamide group or a hydrolysable silane group; and ethylenically unsaturated monomers having at least 2 ethylenically unsaturated double bonds.
- Examples of neutral, non-functional monoethylenically unsaturated monomers M.1 are: esters of acrylic and/or methacrylic acid with alkanols having 1 to 20 C atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2- octyl acrylate, 2-ethylhexyl acrylate, 2-propylpentyl acrylate, n-decyl acrylate, 2- propylheptyl acrylate, Cw isoamyl guerbet acrylate, 1
- C1-C20 alkyl esters of methacrylic acid include, but are not limited to methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-octyl methacrylate, 2-ethylhexyl methacrylate, 2-propylpentyl methacrylate, n- decyl methacrylate, 2-propylheptyl methacrylate, Cw isoamyl guerbet methacrylate, 1 -propylheptyl methacryl
- Preferred monomers M1 are esters of acrylic with alkanols having 1 to 10 C atoms esters of methacrylic acid with alkanols having 1 to 10 C atoms, esters of acrylic with cycloalkanols having 5 to 10 C atoms esters of methacrylic acid with cycloalkanols having 5 to 10 C atoms, furfuryl acrylate, furfuryl methacrylate, vinylaromatic hydrocarbon compounds, specifically styrene, conjugated alkadienes, specifically butadiene, vinyl esters of saturated Ci-Cs alkanoic acids, specifically vinylacetate, and olefins, specifically ethylene and combinations thereof.
- the polymers P are selected from copolymers of a vinylaromatic compound M 1 a, in particular styrene and at least one further monomer M 1 b selected from conjugated aliphatic dienes, alkylesters, in particular Ci-Cio-alkylesters of acrylic acid, alkylesters, in particular Ci-Cw-a Iky I esters of methacrylic acid, cycloalkylesters, in particular Cs-Cw-cy- cloalkylesters of acrylic acid and cycloalkylesters, in particular Cs-Cw-cycloal- kylesters of methacrylic acid and mixtures thereof, e.g.
- the polymers P are selected from styrene-acrylate copolymers, styrenebutadiene copolymers, all-acrylic copolymers, acrylonitrile-acrylate copolymers, vinyl acetate polymers and ethylene-vinylacetate copolymers with particular preference given to styrene-acrylate copolymers and styrene-butadiene copolymers.
- the monomers M which form the polymer P comprise: i. 80 to 99.9% by weight, in particular 85 to 99.5% by weight, based on the total amount of monomers M, of at least one monomer M1 , which is selected from a combination of at least one monovinylaromatic monomer M1 a and at least one further monomer M1 b selected from conjugated aliphatic dienes, alkylesters, in particular Ci-Cw-a Iky I esters of acrylic acid and/or methacrylic acid and cycloalkylesters, in particular Cs-Cw-cycloalkylesters of acrylic acid and/or methacrylic acid and mixtures thereof;
- the monomers M2 are as defined above and preferably selected from primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms, such as acrylamide and methacrylamide, and esters of acrylic and/or methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate.
- primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms such as acrylamide and methacrylamide
- M2 is selected from acrylamide, methacrylamide and esters of methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3- hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate or 4-hydroxybutyl methacrylate.
- M2 is selected from the group consisting of acrylamide, methacrylamide, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
- the monomers M3 are as defined above and preferably selected from methacrylic acid, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acids, and 2- acrylamido-2-methylpropanesulfonic and their salts, in particular their sodium, potassium or ammonium salts, and the monomers of the formula M3c-I, such as mono- (meth)acryloxyethyl phosphate, mono-(meth)acryloxypropyl phosphate, mono- (meth)acryl(oxy-l ,2-ethanediyl)i-2o phosphate and mono-(meth)acryl(oxy-1 ,2- propandiyl)i-2o phosphate and their salts, in particular their sodium, potassium or ammonium salts.
- the monomers M4 are as defined above and preferably selected from the group consisting of the monomers M4a and M4c with particular preference given to monomers M4a bearing a 1 ,3-dicarbonyl moiety, such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, acetoacetoxyethyl methacrylate, and epoxy functionalized (meth)acrylate monomers, such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl acrylate, 3-glycidyloxypropyl methacrylate.
- a 1 ,3-dicarbonyl moiety such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacryl
- a hydrolysable silane group which are in particular selected from vinyltrial- koxysilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane, and methacryloxyalkyltrialkoxysilanes, in particular methacryloxypropyltrimethoxysilane.
- the monomers M which form the polymer P may be of petrochemical origin or may be of bio-renewable sources. In particular at least 30% by weight of the monomers M, preferably at least 40% by weight or at least 50% by weight of the monomers M are based on bio-renewable sources, which means that their content of bio carbon is at least 30 mol-%, in particular at least 40 mol-%, based on the total amount of carbon in the monomers from bio-renewable sources.
- bio-carbon indicates that the carbon is of biological origin and comes from a biomaterial/renewable resources.
- the content in bio-carbon and the content in biomaterial are expressions that indicate the same value.
- a material of renewable origin or biomaterial is an organic material wherein the carbon comes from the CO2 fixed recently (on a human scale) by photosynthesis from the atmosphere.
- a biomaterial Carbon of 100% natural origin
- the isotopic 14 C is formed in the atmosphere and is then integrated via photosynthesis, according to a time scale of a few tens of years at most. The half-life of the 14 C is 5,730 years.
- the materials coming from photosynthesis namely plants in general, necessarily have a maximum content in isotope 14 C.
- the determination of the content of biomaterial or of bio-carbon is can be carried out in accordance with the standards ASTM D 6866-12, the method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
- bio-renewable sources refer to organic materials in which the carbon comes from non-fossil biological sources.
- bio-renewable sources include, but are not limited to, sugars, such as glucose or saccharose, and starches obtained from plants, such as corn, cereals, sugarcanes, beets, potatoes, sweet potatoes or cassava, other polysaccharides of plant origin, such as celluloses, lignocelluoses, hemicelluloses, pectin, chitin, levan and pullulan, plant oils, biomass obtained from plants or agriculturaly waste and the like.
- sugars such as glucose or saccharose
- starches obtained from plants, such as corn, cereals, sugarcanes, beets, potatoes, sweet potatoes or cassava
- other polysaccharides of plant origin such as celluloses, lignocelluoses, hemicelluloses, pectin, chitin, levan and pullulan
- plant oils biomass obtained from plants or agriculturaly waste and the like
- the monomers and monomer precursors such as alcohols and fatty acids, can be directly produced from such biological recources via biological processes, including fermentation and the like.
- Examples of monomers and monomer precursors which can be directly obtained from biorenewable sources are acrylic acid, methacrylic acid, itaconic acid, the alkyl esters and cycloalkyl esters of acrylic acid and methacrylic acid, wherein the at least the carbon atoms of the alkyl and cycloalkyl group, respectively, are of biological origin, i.e. e. they are at least partly made of bio-carbon.
- the respective alkanols and cycloalkanols used for the production of the alkyl esters and cycloalkyl esters of acrylic acid and methacrylic acid preferably have a content of bio-carbon of at least 70 mol-%, based on the total amount of carbon atoms in the respective monomers. This content is advantageously higher, in particular greater than or equal to 80 mol-%, preferably greater than or equal to 90 mol-% and advantageously equal to 100 mol-%.
- itaconic acid, citraconic acid and mesaconic acid can be produced on large scale from renewable materials, e.g. by fermentation of glucose, saccharose, starch or cellulose containing raw materials.
- acrylic acid and methacrylic acid may be produced from biorenewable sources. Further examples are vinyl esters of alkanoic acid, where at least the alkanoic acid is produced from biorenewable sources.
- the polymer content is preferably from 20 to 65% by weight, more preferably from 30 to 60% by weight and in particular from 35 to 55% by weight, based on the total weight of the aqueous composition (II).
- the surface active compound may be an emulsifier, a protective colloid or a mixture of both of them.
- the emulsifier and the protective colloid are distinct from each other by their weight-average molar mass M w .
- An emulsifier has typically a weight-average molar mass M w in general below 2000, while the weight-average molar mass M w of the protective colloid may be up to 50 000, in particular from above 2000 to up to 50000.
- the amount of the surface active compound is in the range from 0.1 to 10% by weight, in partiuclar in the range from 0.5 to 5% by weight, based on the total amount of polymer in the aqueous polymer dispersion.
- the surface active compound comprises one or more emulsifiers.
- the emulsifier is non-ionic, anionic, or cationic. In case of employing a mixture of emulsifiers, their compatibility has to assured, which can be evaluated in case of doubt by preliminary tests.
- an anionic emulsifier is compatible with another anionic emulsifier or a non-ionic emulsifier.
- a cationic emulsifier is typically compatible with another cationic emulsifier or a non-ionic emulsifier.
- the emulsifier is an anionic emulsifier, a combination of two or more anionic emulsifier or a combination of at least one anionic emulsifier and at least one non-ionic emulsifier.
- Examples of customary nonionic emulsifiers are the Emulgin B grades (cetyl/stearyl alcohol ethoxylates, RTM BASF), Dehydrol LS grades (fatty alcohol ethoxylates, EO units: 1-10, RTM BASF), Lutensol A grades (Ci2Ci4-fatty alcohol ethoxylates, EO units: 3-8, RTM BASF), Lutensol AO grades (C13C15-OXO alcohol ethoxylates, EO units: 3-30), Lutensol AT grades (Ci 6 Ci8-fatty alcohol ethoxylates, EO units: 11-80), Lutensol ON grades (Cw-oxo alcohol ethoxylates, EO units: 3-11) and Lutensol TO grades (C -oxo alcohol ethoxylates, EO units: 3-20).
- EO units means the number average of ethylene oxide repeating units in the emulsifier.
- Anionic emulsifiers include for example the alkali metal salts of dialkyl esters of sulfosuccinic acid, the alkali metal salts and the ammonium salt of C8-C12 alkyl sulfates, the alkali metal salts and the ammonium salts of C12-C18 alkylsulfonic acids, the alkali metal salts and the ammonium salts of C9-C18 alkylarylsulfonic acid, the alkali metal salts and the ammonium salts of sulfuric acid monoesters of ethoxylated C12-C18 alkanols (EO units: 4-30) or a sulfuric acid monoester of an ethoxylated (C4-C12 alkyl)phe- nol (EO units: 3-50).
- R a and R b are each a H atom or C4-C24-alkyl and are not both H atoms at the same time, and Mi + and M2 + can be alkali metal ions and/or ammonium, are also useful.
- R a and R b are preferably linear or branched alkyl radicals having from 6 to 18 carbon atoms, in particular 6, 12 or 16 carbon atoms, or hydrogen atoms, where R a and R b are not both hydrogen atoms at the same time.
- Mi + and M2 + are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
- a compound of general formula I, in which Mi + and M2 + are both sodium, R a is a branched alkyl radical having 12 carbon atoms and R b is hydrogen or R a is particularly advantageous.
- Use is frequently made of industrial mixtures which have a proportion of from 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (RTM The Dow Chemical Corp.).
- the compounds of general formula I are commonly known, e.g. from US-A 4 269 749, and commercially available.
- emulsifiers are fatty alcohol phosphates, alkylphenol phosphates, alkyl polyglycol ether phosphates, alkyl polyalkylene oxide phosphates, and fatty alcohol ether phosphates and the salts thereof, in particular the alkalimetal salts and ammonium salts thereof, with particular preference given to the alkalimetal salts such as sodium salts.
- suitable emulsifiers may be found in Houben-Weyl, Methoden der organischen Chemie, volume XIV/1 , Makromolekulare Stoffe, Georg- Thieme-Verlag, Stuttgart, 1961 , pages 192 to 208.
- suitable protective colloids may be non-ionic, anionic or cationic.
- protective colloids are poly(vinyl alcohols), poly(alkylene glycols), poly(acrylic acids) and the alkali metal salt thereof, poly(methacrylic acids) and the alkali metal salt thereof and gelatin derivatives.
- Anionic protective colloid can also be a copolymer, containing a suitable amount of at least one anionic monomer, such as acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, para-vinylphenyl sulfonic acid or salt forms thereof, preferably alkali metal salts thereof, in polymerized form.
- cationic protective colloids are homopolymers and copolymers containing a sufficient amount of cationic monomers, in particular monoethylenically unsaturated monomers having one or more amino groups, which are N-protonated or N-alkylated.
- Examples include N-protonated and N-alkylated derivatives of homopolymers or copolymers of N -vinylform am ide in their at least partly hydrolyzed form, homopolymers or copolymers of N-vinylacetamide in their at least partly hydrolyzed form, N-protonated and N-alkylated derivatives of homopolymers or copolymers of N-vinylcarbazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 1-vinylimidazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 2-vinylimidazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 2-vinylpyridine, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 4-vinylpyridine, N-proton
- the protective colloids are distinct from the polymers dispersed in the aqueous polymer dispersion as they are water-soluble or water dispersible.
- water-soluble or water dispersible is understood that the corresponding protective colloid can be dissolved or dispersed in deionized water at 20°C and 1013 mbar in an amount of at least 10 g/L polymer such that the resulting aqueous solution has either no measurable particle size or a particle size of at most 20 nm as determined by dynamic light scattering in accordance with DIN 22412:2008.
- composition of the invention may moreover contain further auxiliaries, such as
- composition of the invention is formulated as a 2K formulation
- the auxiliaries are generally incorporated in composition (II).
- Flow control agents and defoamers may however also be incorporated in composition (I).
- Suitable wetting agents or dispersants are, for example, sodium, potassium or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers, polyphosphonates, such as sodium 1-hydroxyethane-1 ,1- diphosphonate, and also salts of naphthalenesulfonic acids, more particularly their sodium salts.
- polymeric dispersants such as alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers.
- a metal salt of polyacrylic acid is used.
- the polymeric dispersant is contained in an amount of from 0.1 to 2% by weight, in particular from 0.1 to 1 % by weight, based on the total weight of the polymer of composition (II).
- Acronal® 5400 from BASF SE; aqueous anionic copolymer dispersion of a copolymer of an acrylic acid ester and styrene; solids content: ca. 57%, Tg: -8°C; viscosity (250 s -1 at 23°C; DIN EN ISO 3219): 50-350 mPa-s, pH 5.5-7.5.
- - Acronal 5442® from BASF SE; aqueous, self-cross-linking dispersion of a copolymer of an acrylic acid ester and styrene; solids content: ca. 53.5%, Tg: ca. -15°C; viscosity (100 s -1 at 23°C; DIN EN ISO 3219): 10-100 mPa-s, pH 5.5-8.5.
- 300 g of the formulations were mixed in a 500 ml plastic cup (yoghurt pot). Immediately after mixing, the mass was checked for consistency with a knife spatula. The creaminess and stickiness of the mass was assessed. The dripping from the knife spatula was also assessed. Furthermore, the compound was applied to a concrete block with a 6 mm notched trowel and the processing properties were also assessed.
- compositions A and B given in table 1 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec, whereby slurries were obtained which can be used for producing the water-tight coverings. Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape. The thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel. The film thickness was thus 2.5 mm for wet application.
- compositions A and B given in table 1 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec, whereby slurries were obtained which can be used for producing the water-tight coverings. Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape. The thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel. The film thickness was thus 2.5 mm for wet application.
- compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec. The obtained mixture was directly coated onto a mortar prism according to DIN EN 14891 A8. After coating of a very fine coat (scratch spatula) and drying ( ⁇ 20 min) the first waterproofing coating was applied (thickness 1 .2 mm wet). After drying (approx. 3h) a second layer was coated (thickness also 1 .2 mm wet). For each test formulation a preparation of three samples were done (3 samples for 23°C test, 3 samples for -5°C test and 3 samples for -20°C test).
- the samples obtained in a) were kept at ambient conditions for 28 days and then stored in chlorine water for 7 days.
- Chlorine water was prepared from 200 mg/l NaCI, 200 mg/l of Na2SC>4 and NaOCI kept at a concentration of 0.3 to 0.6 mg/l.
- the pH was kept at 6.5 to 7.8. After storage, the sample was rinsed with water and dried. After drying, tie rod plates were glued and the bond strength was measured as described in b).
- the samples obtained in a) were kept at ambient conditions for 28 days and then stored in 3% by weight aqueous solution of potassium hydroxide for 14 days at 40°C. After storage, the sample was rinsed with water and dried. After drying, tie rod plates were glued and the bond strength was measured as described in b).
- compositions 1 to 6, 8 and 9 showed good water tightness at > 2.5 bar and low water absorption. The test results are summarized in table 7.
- compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed whereby slurries were obtained which can be used for producing the water-tight coverings.
- Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape.
- 300 g of the thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel.
- the film thickness was thus 2.5 mm for wet application.
- the test was performed as follows: A film of the waterproofing composition was applied to a Teflon foil in a layer thickness of 4 mm (dry film thickness). After 28 days of drying, the film was then placed on the slit pressure plate (in contrast to the standard, a rectangular shaped plate of 20x20 cm was used. The slit width was 1 mm and the slit length was 25 mm). A water pressure of 2.5 bar was then applied to the sealing surface for 24 hours.
- the sealing films prepared from all compositions 1 to 9 provided good water tightness, as can be seen from the test results summarized in table 9.
- a waterproofing slurry film of 3mm dry film thickness was produced.
- the film had a width of 50 mm and a length of 200 mm.
- the films and the test mandrel were stored at 0°C for at least 1 h and then the film was slowly bent over the mandrel within 3s. The film must not tear in the process.
- the test results are summarized in table 10.
- the early rain resistance was measured according to DIN EN 15816.
- the waterproofing was applied to a concrete slab in a wet layer thickness of 3 mm. After 4 or 8 hours drying time, the spray water test was carried out. The spraying time was
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Abstract
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| Application Number | Priority Date | Filing Date | Title |
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| EP22176772 | 2022-06-01 | ||
| PCT/EP2023/064472 WO2023232832A1 (en) | 2022-06-01 | 2023-05-31 | Composition for waterproofing membranes |
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| EP (1) | EP4532441A1 (en) |
| CN (1) | CN119301087A (en) |
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| US4269749A (en) | 1979-04-30 | 1981-05-26 | The Dow Chemical Company | Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions |
| DE4003422A1 (en) | 1990-02-06 | 1991-08-08 | Basf Ag | WAITER POLYURETHANE PREPARATIONS |
| CA2043094C (en) * | 1990-06-06 | 1997-02-11 | Robert L. Vecchio | Cement based compositions having elastomeric properties, and method of manufacture |
| CN1120180C (en) | 1994-06-03 | 2003-09-03 | 巴斯福股份公司 | Preparation of aqueous polymer dispersions |
| DE19624299A1 (en) | 1995-06-30 | 1997-01-02 | Basf Ag | Removal of malodorous organic cpds. from dispersion |
| DE19621027A1 (en) | 1996-05-24 | 1997-11-27 | Basf Ag | Continuous removal of monomer from aqueous suspension or dispersion |
| DE19741184A1 (en) | 1997-09-18 | 1999-03-25 | Basf Ag | Reducing residual monomer content of e.g. acrylic polymers |
| DE19741187A1 (en) | 1997-09-18 | 1999-03-25 | Basf Ag | Reducing residual monomer content in aqueous polymer dispersion |
| DE19805122A1 (en) | 1998-02-09 | 1999-04-22 | Basf Ag | Aqueous polymer dispersion useful as binder agent for pigments for interior and exterior paints |
| DE19828183A1 (en) | 1998-06-24 | 1999-12-30 | Basf Ag | Process for removing residual volatile components from polymer dispersions |
| DE19839199A1 (en) | 1998-08-28 | 2000-03-02 | Basf Ag | Process for reducing the amount of residual monomers in aqueous polymer dispersions |
| DE19840586A1 (en) | 1998-09-05 | 2000-03-09 | Basf Ag | Process for reducing the amount of residual monomers in aqueous polymer dispersions |
| DE19847115C1 (en) | 1998-10-13 | 2000-05-04 | Basf Ag | Counterflow stripping tube |
| DE10359703A1 (en) * | 2003-12-18 | 2005-07-14 | Wacker Polymer Systems Gmbh & Co. Kg | Use of biocide-containing, water-redispersible polymer powder compositions in mineral building materials |
| DE102008055064A1 (en) * | 2008-12-22 | 2010-06-24 | Wacker Chemie Ag | Acid-resistant, hydraulically setting compounds |
| JP5628087B2 (en) * | 2010-05-17 | 2014-11-19 | ダウ グローバル テクノロジーズ エルエルシー | Redispersible powder composition for dry mortar formulations |
| DE102010041292A1 (en) * | 2010-09-23 | 2012-03-29 | Wacker Chemie Ag | Flexible, waterproof roof coatings |
| DE202012003354U1 (en) * | 2012-04-03 | 2012-08-31 | Roswitha Weindl-Farnsworth | Mixture for the production of a moldable or pourable mass for the artistic design of objects and surface structures |
| MX2016017135A (en) | 2014-07-01 | 2017-05-10 | Basf Se | A dispersion of (meth)acrylate copolymer containing a hydroxyalkyl (meth)acrylate functional monomer unit for flexible cementitious waterproofing materials. |
| AU2016231286A1 (en) | 2015-03-09 | 2017-09-07 | Basf Se | Flexible cementitious waterproofing slurry |
| ES2928027T3 (en) | 2015-11-10 | 2022-11-14 | Dow Global Technologies Llc | Two-component polymer emulsion compositions for fast-curing, flexible cementitious waterproofing membranes |
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