Copolymer of a carboxylate and a polyether containing polyether side chains of different lengths and its use in a mineral binder composition

Abstract

The present invention relates to a copolymer comprising or consisting of (i) a monomer unit A of general formula (I), (ii) a monomer unit B of general formula (II), and (iii) a monomer unit C of general formula (III). It relates to a copolymer comprising or consisting of JPEG2025523657000012.jpg67160, in particular as a dispersant for mineral binders. The present invention also relates to the use of such a copolymer as a plasticizer for mineral binder compositions. In particular, the copolymers of the present invention have been found to provide a high initial slump flow of the mineral binder composition and to retain its high slump flow over a longer period of time.

Description

Technical Field

[0001] The present invention relates to copolymers comprising structural motifs of at least two polyethers and carboxylates having different chain lengths. The present invention also relates to the use of such copolymers as plasticizers for mineral binder compositions. In particular, the copolymers of the present invention have been found to provide a high initial slump flow for mineral binder compositions and to retain their high slump flow over a longer period.

Background Art

[0002] Copolymers of polycarboxylic acids and alkoxylated ethylenically unsaturated alcohols have been known for many years as dispersing aids for aqueous dispersions, particularly aqueous dispersions of mineral binders. Such polymers are often referred to as polycarboxylate ethers (PCE). PCE functions as a superplasticizer and reduces the water required to achieve a particular level of fluidity of a given uncured mineral binder composition. Reduction of water in mineral binder compositions, particularly cement compositions, is desirable because it reduces segregation of solid components in the uncured composition and increases the compressive strength of the cured composition.

[0003] WO 2016 / 074984 (BASF SE) pamphlet teaches a PCE which is a copolymer having polyether side chains of different lengths, one side chain being short (5 - 35 alkylene oxide repeat units) and the other side chain being significantly longer (45 - 150 alkylene oxide repeat units). In particular, WO 2016 / 074984 pamphlet relates to copolymers derived from alkoxylated hydroxybutyl vinyl ether monomers.

[0004] CN103483504 (Sichuan Tongzhou Chem Tech Co Ltd) discloses a PCE which is a copolymer containing two different alkenyl polyethers, and the copolymer is derived from a mixture of ethoxylated methallyl alcohol and ethoxylated isoprenyl alcohol. Further, when there are units derived from ethoxylated methallyl alcohol, the number of repeating units in the side chain of the copolymer is 32 to 44, and when there are units derived from ethoxylated isoprenyl alcohol, the number of repeating units in the side chain of the copolymer is 52 to 62.

[0005] The PCE-type copolymers described in the prior art are not always the best choice as plasticizers for mineral binder compositions in all cases. One reason is that the mineral binder compositions have a large variation of possible components. Depending on the different mineral binders used, the different aggregates used, the different mixing ratios of the components, etc., different copolymers may be required as plasticizers. This is especially true for the wider use of crushed sand and high-alkali concrete. Another reason is that with many PCE-type copolymers, the generation of compressive strength is reduced, and furthermore, the final compressive strength of the hardened mineral binder composition is decreased. Generally, the decrease in compressive strength is not desirable. Therefore, there is always a need for improved PCE-type copolymers that affect the water requirement and / or the rheology of the mineral binder composition.

Summary of the Invention

Problems to be Solved by the Invention

[0006] The object of the present invention is to provide a PCE-type copolymer suitable as a superplasticizer for mineral binder compositions, particularly cement-based binder compositions. In particular, the PCE-type copolymer should (i) achieve a high initial slump flow of the mineral binder composition at a predetermined mixing ratio with water, and / or (ii) achieve a minimal decrease in the slump flow over time of a predetermined mineral binder composition mixed with water, and / or (iii) It should lead to a higher compressive strength of the hardened mineral binder composition, having the prior art PCE-type copolymer, compared to the same mineral binder composition.

Means for Solving the Problems

[0007] Surprisingly, it has been found that the copolymer according to claim 1 can solve one or more of these purposes.

[0008] In particular, it has been found that a copolymer derived from a combination of an alkoxylated ethylenically unsaturated alcohol having a medium chain length (20 - 60 alkylene oxide repeating units) and an alkoxylated ethylenically unsaturated alcohol having a long chain length (65 - 150 alkylene oxide repeating units) results in a high initial slump flow, good retention of slump flow over time, and an increase in compressive strength. This is particularly applicable when the ethylenically unsaturated alcohol having medium alkoxylation (20 - 60 repeating units) is selected from vinyl alcohol, vinyl-4-hydroxybutyl alcohol, (meth)allyl alcohol or isoprenyl alcohol and when the ethylenically unsaturated alcohol having high alkoxylation (65 - 150 repeating units) is selected from vinyl alcohol or vinyl-4-hydroxybutyl alcohol.

[0009] A further aspect of the invention is the subject matter of the further independent claims. Preferred embodiments of the invention are the subject matter of the dependent claims.

Mode for Carrying Out the Invention

[0010] In a first aspect, the invention relates to (i) General formula (I)

Chemical formula

Chemical formula

Chemical formula

[0011] The copolymer of the present invention is (i) General formula (Ia)

Chemical formula

Chemical formula

Chemical formula

[0012] Suitable methods for producing the copolymers of the present invention by coincidence are known to those skilled in the art. In particular, copolymerization is a process of radical polymerization of different monomers. Suitable conditions for the process of radical polymerization are described, for example, in Examples 1 to 1 of European Patent No. 1103570 (Nippon Shokubai Chem Ind) or in Example 1 of International Publication No. 2012 / 084954 Pamphlet (Sika Technology AG). However, other methods of radical polymerization are equally suitable.

[0013] According to some embodiments, the copolymerization is carried out in the presence of an initiator for radical polymerization at a reaction temperature of 10 °C to 50 °C, preferably 15 °C to 35 °C. The term "initiator for radical polymerization" or "radical initiator" herein is defined as a compound described as a suitable initiator for radical polymerization in CD Rompp Chemie Lexikon, 9th edition, version 1.0, Georg Thieme Verlag, Stuttgart 1995. In particular, the copolymerization is carried out in the presence of a mixture of iron(II) sulfate, iron hypophosphite, hydrogen peroxide and sodium hydroxymethanesulfinate.

[0014] The copolymers of the present invention can be random copolymers or can have a block unit arrangement or a gradient arrangement of monomers.

[0015] The monomer unit A of the general formula (I) is preferably derived from ethoxylated, propoxylated and / or butoxylated vinyl alcohol, allyl alcohol, methallyl alcohol, isoprenyl alcohol and 4-hydroxybutyl vinyl ether. The monomer unit of the general formula (I) can carry only ethylene oxide groups, only propylene oxide groups or only butylene oxide groups. The monomer unit A of the general formula (I) can equally carry a combination of ethylene oxide groups, propylene oxide groups and / or butylene oxide groups, for example a combination of ethylene oxide and propylene oxide groups or a combination of ethylene oxide and butylene oxide groups.

[0016] Suitable monomer units of general formula (II) are preferably derived from ethoxylated, propoxylated and / or butoxylated vinyl alcohol and 4-hydroxybutyl vinyl ether. The monomer unit B of general formula (II) can carry only ethylene oxide groups, or only propylene oxide groups, or only butylene oxide groups. The monomer unit B of general formula (II) can equally carry a combination of ethylene oxide groups, propylene oxide groups and / or butylene oxide groups, for example a combination of ethylene oxide and propylene oxide groups or a combination of ethylene oxide and butylene oxide groups.

[0017] According to a preferred embodiment, in the copolymers of the invention, at least 66 mol%, preferably at least 75 mol%, more preferably at least 90 mol%, particularly at least 99 mol% of the alkylene groups A in general formulas (I) and (II) are ethylene groups.

[0018] Particularly preferably, in relation to the present invention, the monomer unit A of general formula (I) is derived from ethoxylated vinyl alcohol or ethoxylated methallyl alcohol with an ethoxylation degree of 40 to 60.

[0019] Particularly preferably, in relation to the present invention, the monomer unit B of general formula (II) is derived from ethoxylated vinyl alcohol or ethoxylated 4-hydroxybutyl vinyl ether with an ethoxylation degree of 120 to 140.

[0020] Suitable monomer units of general formula (III) are derived from acrylic acid and methacrylic acid and their salts with alkali metals, alkaline earth metals, ammonium or organic ammonium groups.

[0021] Thus, according to the embodiment, suitable monomer Aa is ethoxylated, propoxylated and / or butoxylated vinyl alcohol, allyl alcohol, methallyl alcohol, isoprenyl alcohol and 4-hydroxybutyl vinyl ether, suitable monomer Bb is ethoxylated, propoxylated and / or butoxylated vinyl alcohol and 4-hydroxybutyl vinyl ether, and suitable monomer Cc is acrylic acid, methacrylic acid and / or maleic acid and salts thereof of alkali metals, alkaline earth metals, ammonium or organic ammonium groups. Naturally, it is also possible to use a mixture of two or more different acids as monomer Cc. According to the embodiment, monomer Cc is acrylic acid. According to a further embodiment, monomer Cc is methacrylic acid. According to a further embodiment, monomer Cc is maleic acid. According to a further embodiment, monomer Cc is a mixture of acrylic acid and methacrylic acid. According to a further embodiment, monomer Cc is a mixture of acrylic acid and maleic acid. According to a further embodiment, monomer Cc is a mixture of methacrylic acid and maleic acid. According to a further embodiment, monomer Cc is a mixture of acrylic acid, methacrylic acid and maleic acid.

[0022] According to other embodiments, in the general structures (I)-(III) of the copolymer of the present invention, R 0 is methyl, R 1 and R 2 are H, A is ethylene, R u is H or methyl, R v is H or COOM, M is selected from H, alkali metals, alkaline earth metals or organic ammonium groups, x = 1, y = 0, n = 20-40, o = 0 or 1, and p = 65-140.

[0023] According to the embodiment, in the general structures (I)-(III) of the copolymer of the present invention, R 0 is methyl, R 1 and R 2 are H, A is ethylene, R uis H or methyl, and R v is H or COOM, M is selected from H, an alkali metal, an alkaline earth metal or an organic ammonium group, x = 1, y = 0, n = 40 to 60, o = 0 or 1, and p = 65 to 140.

[0024] According to another embodiment, in the general structures (I) to (III), the copolymer of the present invention has R 0 , R 1 and R 2 being H, A being ethylene, R u being H or methyl, R v being H or COOM, M being selected from H, an alkali metal, an alkaline earth metal or an organic ammonium group, x = 0, y = 0 or 1, n = 20 to 40, o = 0 or 1, and p = 65 to 140.

[0025] According to another embodiment, in the general structures (I) to (III), the copolymer of the present invention has R 0 , R 1 and R 2 being H, A being ethylene, R u being H or methyl, R v being H or COOM, M being selected from H, an alkali metal, an alkaline earth metal or an organic ammonium group, x = 0, y = 0 or 1, n = 40 to 60, o = 0 or 1, and p = 65 to 140.

[0026] The molar ratio of the monomer units of the structural formulas (I), (II) and (III) in the copolymer of the present invention can be represented as a molar ratio a:b:c. Here, a means the molar fraction of the monomer unit A of the structural formula (I), b means the molar fraction of the monomer unit B of the structural formula (II), and c means the molar fraction of the monomer unit C of the structural formula (III).

[0027] According to an embodiment, the copolymer of the present invention is characterized in that the molar ratio a:b:c is in the range of 0.01 to 0.9:0.9 to 0.01:1, preferably in the range of 0.04 to 0.5:0.5 to 0.06:1, particularly in the range of 0.03 to 0.08:0.09 to 0.12:1.

[0028] Generally, it is preferable that the molar ratio of monomer unit C is higher than the molar ratio of monomer unit A and / or monomer unit B. In a specific embodiment, the copolymer of the present invention is characterized in that the ratio of monomer unit C to all monomer units constituting the copolymer is 50 to 99 mol%, preferably 66 to 99 mol%, particularly 75 to 99 mol%.

[0029] According to an embodiment, the copolymer of the present invention has a molar ratio of monomer unit A to monomer unit B that exceeds 0.1, preferably exceeds 0.5, more preferably exceeds 1, and particularly exceeds 3.

[0030] The molecular weight M of the copolymer of the present invention w can be measured by GPC using PEG as a standard substance and can be in the range of 5000 to 200000 g / mol, preferably 10000 to 150000 g / mol.

[0031] Optionally, the copolymers of the present invention may contain additional monomer units different from monomer units A, B or C. According to an embodiment, the copolymers of the present invention are esters of (meth)acrylic acid, in particular hydroxyalkyl esters of (meth)acrylic acid, such as 2-hydroxyethyl acrylate or 3-hydroxypropyl acrylate, (meth)acrylamide and its alkylamides, 2-acrylamido-2-methylpropanesulfonic acid, alkylene phosphates or phosphonates, in particular vinyl phosphate, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth)allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl butyl ether, 3-methyl-3-buten-1-ol, styrene and / or butadiene, and may further contain monomer units derived from monomers selected therefrom.

[0032] When such additional monomer units are present, their molar ratio is preferably 33 mol% or less, more preferably 25 mol% or less, based on all monomer units of the copolymer. In general, it is preferably that the copolymers of the present invention do not essentially contain additional monomer units other than monomer units A, B and C. Particularly preferably, the copolymers of the present invention consist of monomer units A, B and C.

[0033] According to an embodiment, the copolymers of the present invention are in a liquid state, preferably a dispersion or solution in water. Such a dispersion or solution in a liquid, preferably in water, is obtained by directly copolymerizing the respective monomers in a liquid, preferably in water. It is also possible to disperse or dissolve the copolymers of the present invention in a liquid, preferably in water, to obtain a dispersion or solution of the copolymer.

[0034] According to other embodiments, the copolymer of the present invention is in a solid state at 25 °C and 1023 millibars. The solid state is preferably a free-flowing powder or flakes. Such a copolymer in solid state can be particularly useful when it is mixed with other dry components to form dry concrete or dry mortar. The storage life of such dry concrete or dry mortar can be improved when the copolymer of the present invention is used therein in solid state.

[0035] The means for producing the copolymer of the present invention in solid state is not particularly limited and is known per se to those skilled in the art. Such means include spray drying, oven drying, flaking, etc. of a dispersion or solution of the copolymer in a liquid.

[0036] In a second aspect, the present invention relates to the use of the above-described copolymer as an admixture in a mineral binder composition.

[0037] All of the above embodiments also apply to this aspect.

[0038] In relation to the present invention, a mineral binder composition is a composition containing at least one mineral binder. The mineral binder is in particular a hydraulic binder (e.g., cement or hydraulic lime), a latent hydraulic binder (e.g., slag), a pozzolanic binder (e.g., fly ash, clay) or a non-hydraulic binder (e.g., gypsum plaster or plaster).

[0039] According to an embodiment, the mineral binder composition comprises a hydraulic binder, preferably cement. Cement having a cement clinker content of ≧ 35 wt% is particularly preferred. In particular, the cement is a CEM I, II, III, IV or V type cement according to EN 197-1 standard or a calcium aluminate cement or calcium sulfoaluminate cement according to EN 14647:2006-01 standard or a mixture thereof. The proportion of the hydraulic binder in the total mineral binder is advantageously at least 5 wt%, particularly at least 20 wt%, preferably at least 35 wt%, particularly at least 65 wt%. In a further advantageous embodiment, the mineral binder consists of a hydraulic binder, particularly cement clinker, up to about at least 95 wt%.

[0040] In an advantageous embodiment, the cement further contains up to 40 wt%, preferably up to 35 wt%, particularly up to 20 wt% of calcium sulfate based on the total dry weight of the cement. The calcium sulfate may be present in the form of calcium sulfate hemihydrate, calcium sulfate dihydrate and / or anhydrite.

[0041] According to a further embodiment, the mineral binder composition comprises, in addition to or instead of the hydraulic binder, other binders. These are particularly latent hydraulic binders and / or pozzolanic binders. Suitable latent hydraulic and / or pozzolanic binders are, for example, slag, clay, particularly calcined clay, fly ash, silica dust, silica fume, rice husk ash, burnt shale, trass and pumice. In an advantageous embodiment, the mineral binder contains 5 to 95 wt%, particularly 5 to 65 wt%, particularly 15 to 35 wt% of latent hydraulic and / or pozzolanic binders based on the total dry weight of the mineral binder.

[0042] The mineral binder composition of the present invention can also be based on calcium sulfate and / or lime as the mineral binder. Calcium sulfate means including any of anhydrite, α and β calcium sulfate hemihydrates and / or calcium sulfate dihydrate. Lime means including any of hydraulic lime, air-hardening lime and / or natural hydraulic lime.

[0043] The copolymer of the present invention is used in the mineral binder composition in an amount of 0.01% to 10% by weight, preferably 0.1% to 2% by weight, based on the total weight of the mineral binder.

[0044] In another aspect, therefore, the present invention also relates to a mineral binder composition comprising at least one mineral binder and the above-mentioned copolymer in an amount of 0.01% to 10% by weight, preferably 0.1% to 2% by weight, based on the total weight of the mineral binder.

[0045] The mineral binder composition of the present invention may also contain further components. Preferably, such further components are selected from at least one of aggregate, filler, additive and water.

[0046] The term aggregate used in connection with the present invention means a mineral material that is non-reactive in the hydration reaction of the mineral binder. The aggregate can be any aggregate commonly used in cementitious materials such as concrete, mortar, screed, render, grout, coating, putty, etc. Common aggregates are, for example, rock, crushed stone, gravel, limestone, sand, recycled concrete, perlite or vermiculite.

[0047] In connection with the present invention, a filler is a fine-grained mineral additive that does not have cementitious properties. A common filler is finely ground calcium carbonate.

[0048] The additive can be an additive commonly used in the concrete or mortar industry. Common additives include plasticizers, thickeners, setting retarders, air entrainers, deaerators, corrosion inhibitors, fibers, expansion-generating additives, pigments, strength enhancers, waterproof additives, alkali-aggregate reaction inhibitors, chromate reducers, and / or antibacterial agents.

[0049] According to an embodiment, the mineral binder composition of the present invention is characterized by further comprising at least one of aggregate, filler, additive, and water.

[0050] The copolymer of the present invention has the effect of increasing the initial slump flow and / or maintaining the slump flow of the mineral binder composition over a long period. The slump flow can be measured according to the EN12350-5 standard.

[0051] In particular, the slump flow of the mineral binder composition containing the copolymer of the present invention, although containing a polycarboxylic acid ether type copolymer, increases initially and / or is maintained for a longer period compared to the same mineral binder composition not according to the present invention. Therefore, the copolymer of the present invention is used as an admixture for the mineral binder composition to increase the initial slump flow and / or improve the retention of slump flow over time.

[0052] Therefore, the present invention also relates to a method for increasing the slump flow of a mineral binder composition, (i) providing a mineral binder or a mineral binder composition; (ii) providing the above-mentioned polymer; (iii) mixing the copolymer and the mineral binder or the mineral binder composition and including the method.

[0053] The use of the mineral binder composition of the present invention is not particularly limited. Generally, the mineral binder composition of the present invention can be used as concrete, mortar, screed, render, plaster, grout, adhesive, waterproof membrane, substrate, or waterstop.

[0054] Thus, in another aspect, the present invention also relates to the use of the above mineral binder composition as concrete, mortar, screed, render, plaster, grout, adhesive, waterproof membrane, substrate or water stop plug.

Examples

[0055] Production of Copolymer CP-1 The copolymer was produced by radical polymerization. Thus, 500 g of methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol), 53 g of acrylic acid and 500 g of water were charged into a glass reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser. 1.25 g of a 10% aqueous solution of iron(II) sulfate·7H2O and 1.7 g of sodium hypophosphite were added. The mixture was heated to 35°C, and then 8.5 g of a 30% aqueous solution of hydrogen peroxide and 3.5 g of a 5% aqueous solution of sodium hydroxymethanesulfinate were slowly added dropwise. After the addition was completed, the reaction temperature was maintained at 40°C for 120 minutes. The resulting mixture was cooled to below 30°C and neutralized with NaOH. A transparent viscous solution of polymer CP-1 was obtained. Polymer CP-1 is a comparative polymer and not according to the present invention.

[0056] Production of Copolymer CP-2 Methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol) was replaced with 500 g of vinyloxybutyl polyethylene glycol (OH-terminated, M w = 6000 g / mol), and copolymer CP-2 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer CP-2 was obtained. Polymer CP-2 is a comparative polymer and not according to the present invention.

[0057] Production of Copolymer CP-3 Methallyl polyethylene glycol (OH-terminated, M wInstead of 500 g of vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 3000 g / mol), 38 parts by weight of vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 600 g / mol) and 62 parts by weight of a mixture of 210 g were used, and copolymer CP-3 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer CP-3 was obtained. Polymer CP-3 is a comparative polymer and is not according to the present invention.

[0058] Production of Copolymer CP-4 Methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol), instead of 500 g, vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 3000 g / mol) 736 g was used, and copolymer CP-4 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer CP-4 was obtained. Polymer CP-4 is a comparative polymer and is not according to the present invention.

[0059] Production of Copolymer CP-5 Methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol), instead of 500 g, vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 3000 g / mol) 20 parts by weight and vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 6000 g / mol) 80 parts by weight of a mixture of 500 g were used, and copolymer CP-5 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer P-5 was obtained. Polymer P-5 is a comparative polymer and is not according to the present invention.

[0060] Production of Copolymer P-1 Methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol), instead of 500 g, methallyl polyethylene glycol (OH-terminated, M w= 2400 g / mol) 80 parts by weight, and 500 g of a mixture with 20 parts by weight of vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 3000 g / mol) were used, except for this, copolymer P-1 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer P-1 was obtained. Polymer P-1 is a polymer according to the present invention.

[0061] Production of Copolymer P-2 Methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol), instead of 500 g, 50 parts by weight of methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol) and 50 parts by weight of a mixture with 500 g of vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 3000 g / mol) were used, except for this, copolymer P-2 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer P-2 was obtained. Polymer P-2 is a polymer according to the present invention.

[0062] Production of Copolymer P-3 Methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol), instead of 500 g, 20 parts by weight of methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol) and 80 parts by weight of a mixture with 500 g of vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 6000 g / mol) were used, except for this, copolymer P-3 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer P-3 was obtained. Polymer P-3 is a polymer according to the present invention.

[0063] Production of Copolymer P-4 Methallyl polyethylene glycol (OH-terminated, M w = 2400 g / mol), instead of 500 g, vinyl oxybutyl polyethylene glycol (OH-terminated, M w = 6000 g / mol) 15 parts by weight, and isoprenyl polyethylene glycol (OH-terminated, Mw Copolymer P-4 was produced in the same manner as copolymer CP-1, except that 650 g of a mixture with 85 parts by weight of methallyl polyethylene glycol (OH-terminated, M = 2400 g / mol) was used. A transparent viscous solution of polymer P-4 was obtained. Polymer P-4 is a polymer according to the present invention.

[0064] Production of Copolymer P-5 Methallyl polyethylene glycol (OH-terminated, M w Instead of 500 g of vinyl oxybutyl polyethylene glycol (OH-terminated, M = 2400 g / mol), 620 g of a mixture of 25 parts by weight of vinyl oxybutyl polyethylene glycol (OH-terminated, M = 3000 g / mol) and 75 parts by weight of isoprenyl polyethylene glycol (OH-terminated, M = 2400 g / mol) was used, and copolymer P-5 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer P-5 was obtained. Polymer P-5 is a polymer according to the present invention. w = 3000 g / mol) 25 parts by weight and isoprenyl polyethylene glycol (OH-terminated, M w = 2400 g / mol) 75 parts by weight was used, and copolymer P-5 was produced in the same manner as copolymer CP-1. A transparent viscous solution of polymer P-5 was obtained. Polymer P-5 is a polymer according to the present invention.

[0065] Production of Test Mortar Mortars C1 - C5 and E1 - E5 were prepared by mixing 750 g of cement (CEM I 52.5R commercially available from Vigier), 141 g of limestone filler, 738 g of sand (0 - 1 mm), 1107 g of sand (1 - 4 mm) and 1154 g of sand (4 - 8 mm) in a dry state for 1 minute in a Hobart mixer at 25 °C. Then, each copolymer and water shown in Table 1 below were added within 30 seconds. The amount of copolymer added was 1% by weight with respect to the cement in all cases, and this 1% by weight was related to the dry matter of the copolymer aqueous solution, i.e., related to the actual amount of each copolymer added. The amount of water added was such that a water-to-cement weight ratio (w / c ratio) of 0.39 was obtained. The amount of water added together with the copolymer aqueous solution was also calculated with respect to this w / c ratio. Then, mixing was continued for 2.5 minutes. Mortar compositions C1 - C5 are for comparison and are not compositions according to the present invention, while mortar compositions E1 - E5 are compositions according to the present invention.

[0066] The copolymers tested had different ratios of monomer units A, B, and C (varying molar ratios a:b:c). However, the packing density of the copolymers tested was 1.3 in all cases. The packing density of the copolymer is calculated from each molar ratio a:b:c and the moles of COOH groups per polymer (g).

[0067] The slump flow of each cement paste (abbreviated as S.F. in Table 1) was measured according to EN12350-5 after the time shown in Table 1. The cement paste was premixed for 30 seconds before measurement.

[0068] The compressive strength (abbreviated as C.S. in Table 1) was measured according to EN12190 on 4×4×16 cm prisms after the time shown in Table 1 below.

[0069] The curing time was estimated from the cumulative heat flow curve determined by integrating the heat flow curve measured in an isothermal process described in ASTM C1702-17 using a commercially available i-CAL8000 device from Calmetrix. The curing time is the time when the cumulative heat flow curve reaches a plateau.

[0070] The results are shown in Table 1 below.

[0071]

Table 1

[0072] From the results in Table 1, it can be seen that the prior art polymer provides satisfactory initial slump flow, but shows a significant decrease in slump flow over time and also shows relatively low compressive strength (see Comparative Example C1). The prior art polymer with long side chains can increase the compressive strength, but also shows a reduction in initial slump flow (see C2 and C4 relative to Comparative Example C1). The copolymer of the present invention was able to increase the initial slump flow while maintaining a relatively high compressive strength compared to the prior art copolymers (see Examples E1 - E5). At the same time, when the copolymer of the present invention was used, the decrease in slump flow over time was at a level that was completely acceptable for practical applications and was at a lower level compared to the prior art copolymers. The comparative copolymer CP - 4 showed an increase in slump flow over time, which is often not required. For copolymers with short side chains that do not have sufficient length (e.g., only approximately 13 EO units in CP - 3), sufficient slump flow and initial strength could not be obtained (see Comparative Example C3).

Claims

1. Dispersants for copolymers, particularly mineral binders, including the following: (i) A monomer unit A of general formula (I), 【Chemistry 1】 During the ceremony, R ０ is H or methyl, and R １ These are H, C1-C20 alkyl, aralkyl, or aryl. A is an alkylene group having 2 to 4 carbon atoms. x = 0, 1, or 2, y = 0 or 1, and, n = 20 to 60, preferably 40 to 60. Monomer unit A; (ii) A monomer unit B of general formula (II), 【Chemistry 2】 During the ceremony, R ２ These are H, C1-C20 alkyl, aralkyl, or aryl. A is an alkylene group having 2 to 4 carbon atoms. o = 0 or 1, and, p = 65 to 150, preferably 120 to 140. Monomer unit B, and (iii) A monomer unit C of general formula (III), 【Transformation 3】 During the ceremony, they acted independently of each other. R ｕ is H or methyl, R ｖ is H or COOM, M is selected from H, alkali metals, alkaline earth metals, ammonium, or organic ammonium groups. Monomer unit C, It includes or consists of the structural formulas (I), (I), and (III). ＊ This represents a copolymer, specifically a binding site to the polymer chain.

2. In the general structures (I) to (III), R ０ is methyl, R １ and R ２ are H, A is ethylene, R ｕ is H or methyl, R ｖ is H or COOM, M is selected from H, an alkali metal, an alkaline earth metal or an organic ammonium group, x = 1, y = 0, n = 40 to 60, o = 0 or 1, and p = 65 to 140, The copolymer according to claim 1, characterized in that.

3. In the above general structures (I) to (III), R ０ , R １ and R ２ H is H, A is ethylene, and R ｕ is H or methyl, and R ｖ The copolymer according to claim 1, characterized in that is H or COOM, M is selected from H, alkali metals, alkaline earth metals or organic ammonium groups, x = 0, y = 0 or 1, n = 40 to 60, o = 0 or 1, and p = 65 to 140.

4. The copolymer according to claim 1, wherein at least 66 mol%, preferably at least 75 mol%, more preferably at least 90 mol%, and particularly at least 99 mol%, of the alkylene group A in general formulas (I) and (II) is an ethylene group.

5. The copolymer according to any one of claims 1 to 4, characterized in that the molar ratio of the monomer units a:b:c is in the range of 0.01 to 0.9:0.9 to 0.01:1, preferably in the range of 0.04 to 0.5:0.5 to 0.06:1, and particularly in the range of 0.03 to 0.08:0.09 to 0.12:

1.

6. The copolymer according to any one of claims 1 to 4, further comprising units derived from monomers selected from esters of (meth)acrylic acid, particularly hydroxyalkyl esters of (meth)acrylic acid, such as 2-hydroxyethyl acrylate or 3-hydroxypropyl acrylate, (meth)acrylamide and its alkylamide, 2-acrylamide-2-methylpropanesulfonic acid, alkylene phosphate or phosphonate, particularly vinyl phosphate, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth)allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl butyl ether, 3-methyl-3-buten-1-ol, styrene, and / or butadiene.

7. The copolymer according to any one of claims 1 to 4, characterized in that the copolymer is in powder form.

8. The copolymer according to any one of claims 1 to 4, characterized in that the copolymer is in the form of a dispersion or solution in a liquid, preferably in water.

9. The copolymer according to any one of claims 1 to 4, characterized in that the ratio of monomer unit c to all monomers constituting the copolymer is 50 to 99 mol%, preferably 66 to 99 mol%, and particularly 75 to 99 mol%.

10. The copolymer according to any one of claims 1 to 4, characterized in that the molar ratio of monomer unit a to monomer unit b is greater than 0.1, preferably greater than 0.5, more preferably greater than 1, and particularly greater than 3.

11. Use of the copolymer according to any one of claims 1 to 4 as an admixture in a mineral binder composition.

12. A mineral binder composition comprising at least one mineral binder and a copolymer according to any one of claims 1 to 4 in an amount of 0.01% to 10% by weight, preferably 0.1% to 2% by weight, relative to the total weight of the mineral binder.

13. The mineral binder composition according to claim 12, further comprising at least one of aggregate, filler, additive, and water.

14. Use of the mineral binder composition according to claim 12 as concrete, mortar, screed, renderer, plaster, grout, adhesive, waterproof membrane, underlayment, or stopcock.

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