GB2279655A - Additives for cement compositions - Google Patents

Additives for cement compositions Download PDF

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Publication number
GB2279655A
GB2279655A GB9313759A GB9313759A GB2279655A GB 2279655 A GB2279655 A GB 2279655A GB 9313759 A GB9313759 A GB 9313759A GB 9313759 A GB9313759 A GB 9313759A GB 2279655 A GB2279655 A GB 2279655A
Authority
GB
United Kingdom
Prior art keywords
cementiferous
compositions
copolymer
additive
methyl methacrylate
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.)
Withdrawn
Application number
GB9313759A
Other versions
GB9313759D0 (en
Inventor
J Dolan
D Carter
S Moreton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
Unilever PLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC filed Critical Unilever PLC
Priority to GB9313759A priority Critical patent/GB2279655A/en
Publication of GB9313759D0 publication Critical patent/GB9313759D0/en
Publication of GB2279655A publication Critical patent/GB2279655A/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials

Abstract

An additive composition, for cementiferous compositions, based on a copolymer, of acrylic acid and methyl methacrylate (or salt thereof) mixed with lignosulphonate dramatically increases both the flow characteristics of the cementiferous compositions and the water reduction of said cementiferous compositions while maintaining other properties within satisfactory limits. The copolymer comprises 40 - 90 mole % acrylic acid and 10 - 60 mole % methyl methacrylate.

Description

Cementiferous comno tions Ffeld of the invention The present invention relates to cementiferous compositions and to additives for use in such compositions, which additives improve the physical characteristics of the cementiferous compositions.
Background of the invention The cementiferous compositions with which this invention is concerned include concretes which comprises cement, coarse and fine aggregates and water; cement pastes which comprise cement and water and mortars which comprise cement, sand and water; lime sand and water, or mixtures containing both lime and cement. The invention is also applicable to steam-cured concretes comprising cement, aggregate and water; lime or limestone and siliceous materials such as silica flour and water.
Various additives for use in cementiferous compositions have been previously proposed including for example lignosulphonates, naphthalene sulphonates and water soluble melamine formaldehyde condensates.
Also various polymeric materials have been evaluated as plasticiser additives for cementiferous compositions EP-B-0137582 (Unilever), discloses additive compositions for cementiferous compositions comprising an aqueous solution of a copolymer comprising an ethylenically polymerisable carboxylic acid and an ethylenically unsaturated monomer having a hydroxyl functional group. It is disclosed in this document that dispersants such as lignosulphonates, naphthalene sulphonates or water-soluble melamine formaldehyde polymers can be added.
US-A-5047087 (National Starch and Chemical) discloses additive compositions for cementiferous compositions comprising an ethylenically polymerisable carboxylic acid and an alkyl ester of an ethylenically polymerisable carboxylic acid. This document discloses additive compositions based on acrylic acid and methyl methacrylate.
It has now been discovered that an additive composition, for cementiferous compositions, based on a copolymer, of acrylic acid and methyl methacrylate, mixed with lignosulphonates dramatically increases both the flow characteristics of the cementiferous compositions and the water reduction of said cementiferous compositions while maintaining other properties within satisfactory limits.
General descsition of she invention It is a first object of the present invention to provide an additive for cementiferous compositions comprising: a) an aqueous solution of a copolymer or a soluble salt thereof, comprising from 40 to 90 mole% of acrylic acid and from 10 to 60 mole% of methyl methacrylate, b) lignosulphonates, It is a second object of the present invention to provide a cementiferous composition comprising as an additive an aqueous mixture of: a) an aqueous solution of a copolymer or a soluble salt thereof, comprising from 40 to 90 mole% of acrylic acid and from 10 to 60 mole% of methyl methacrylate, b) lignosulphonates.
The water content of the aqueous solution of copolymer can be between 40 and 70% by weight.
Examples of lignosulphonates are derived from fermented and fractionated spruce sulphite liquor. The preferred lignosulphonate is the sodium or calcium salt with reducing sugars below 10% by weight.
The amount of lignosulphonates used in a cementiferous composition of the present invention is preferably in the range 0.1 to 1 % by weight based on solids content of said cementiferous composition.
Absolute molecular weight of the copolymers of this invention have not been determined. However, apparent molecular weight, as calculated relative to polyethylene glycol standards have been determined using gel permeation chromatography. The apparent molecular weight of the copolymer may be varied over a wide range, the preferred range being 1,000 to 15,000.
The amount of copolymer used in a cementiferous composition of the present invention is preferably in the range 0.05 to 0.8 % by weight based on solids content of said cementiferous composition.
Therefore the weight ratio (lignosulphonates/copolymer) in the additive is between 20:1 and 1:8 preferably between 2.5:1 and 1:1.
Suitable copolymers may be made by the copolymerization of acrylic acid with methyl methacrylate using methods known in polymerisation technology. The resultant copolymer may be neutralised up to pH 7 with a suitable base such as sodium hydroxide or other soluble base and diluted with water to the required concentration for use in the cementiferous composition provided by this invention.
Tests. definitions and Procedures i) Slump test The test was carried on according to British Standard BS 1881 Part 102.
ii) Flow The test was carried on according to British standard BS 1881 Part 105 iii) Plastic density The test was carried on according to British Standard BS 1881 Part 107.
iv) Compressive strength The test was carried on according to British Standard BS 1881 Part 116, v) Water reduction The test was carried on according to British Standard BS 5075.
vi) Mix design Portland Cement ( Blue Circle 7) 400 kg/m3 20 mm Natural agregate 850 kg/m3 10 mm Natural agregate 370 kg/m3 Sand 560 kg/m3 Free water/Cement ratio 0.47 Specific descrition of the invention The present invention will be further described in the following examples.
Different tests have been done using different additive compositions added at different doses to concrete using the same design as earlier described. They were always compared with a control, i.e. a concrete to which no additive was added.
The various tested additive compositions are described below. All the additive compositions had a solids content of 308 by weight.
Invention: - Acrylic acid/methyl methacrylate copolymer solution 60% water - 34% acrylic acid - 6% methyl methacrylate).
- Calcium Lignosulphonate.
Comp: - Acrylic acid/methyl methacrylate copolymer solution ( 608 water - 34% acrylic acid - 6% methyl methacrylate).
Comp2: - Sodium naphthalene sulphonate Comp3: - Sodium salt of sulphonated melamine formaldehyde resin.
Comp4 - Calcium lignosulphonate.
In a first series of tests, different dose of additives were added and the influence on flow and compressive strength was assessed. The results are summarized in Tables Ia, Ib, Ic.
The slump figures are only given for the control since the addition of a plasticizer makes a slump figure meaningless.
Table Ia
Admixture Dose Slump Flow Plastic Compressive (%) (mm) (cm) Density Strength (N/mm2) (kg/m3) 1 day 7 days Control 55 2370 21.4 45.0 Invention 1 66 2350 15.4 43.4 Comp1 1 60 2380 17.1 46.1 Comp2 1 61 2370 18.6 43.1 Comp3 1 57 2360 19.0 40.4 Comp4 1 57 2340 14.0 39.6 Table Tb
Admixture Dose Slump Flow Plastic Compressive (%) (mm) (cm) Density Strength (N/mm2) (kg/m3) 1 day 7 days Control 70 39 2370 17.3 43.8 Invention 0.5 58 2370 16.2 43.3 Compl 0.5 56 2370 15.1 45.4 Comp2 0.5 50 2350 16.5 42.6 Comp3 0.5 49 2360 14.8 41.9 Comp4 0.5 55 2320 17.7 41.0 Table Ic
Admixture Dose Slump Flow Plastic Compressive (%) (mm) (cm) Density Strength (N/rnm2) (kg/m3) 1 day 7 days Control 80 44 2370 18.2 43.4 Invention 1.5 64 2360 12.4 44.6 Comp1 1.5 62 2360 Comp2 1.5 63 2360 20.0 46.4 Comp3 1.5 64 2370 22.2 48.2 Comp4 1.5 62 2320 16.8 43.4 Having established that the additive of the present invention gives much better flow for dose of 0.58 to 1% and at least equal flow for dose of up to 1.5%, the water reduction as well as the compressive strength were assessed at constant slump of 85 mm +/- 5mm. The results are summarized in Table II.
Lble II
Admixture Dose Slump Water Compressive (%) (mum) Reduction Strength (%) (N/mm2) 1 day Control 90 20.2 Invention 1 85 14 27.7 Compl 1 80 12 25.9 Comp2 1 90 8 26.0 Comp3 1 90 6 23.5 Comp4 1 80 8 23.6 It is clear that it is the concrete using the additive of the present invention which gives the best water reduction together with the best compressive strength. Therefore, the synergistic effect of the acrylic acìd/methyl methacrylate copolymer on the one hand and lignosulphonate on the other hand is completely proven.

Claims (2)

  1. Claims
    1- Additive for cementiferous compositions comprising: a) an aqueous solution of a copolymer or a soluble salt thereof, comprising from 40 to 90 mole% of acrylic acid and from 10 to 60 mole% of methyl methacrylate, b) lignosulphonate.
    2- Additive according to claim 1 wherein the weight ratio (lignosulphonate/copolymer) in the additive is between
  2. 2.5:1 and 1:1.
    3- Cementiferous composition comprising an additive according to claim 1 or 2.
    4- Cementiferous composition according to claim 3 .comprising 0.05 to 0.8 % by weight, based on solids content of said cementiferous composition, of acrylic acid/methyl methacrylate copolymer.
    5- Cementiferous composition according to claim 3 comprising 0.1 to 1 % by weight, based on solids content of said cementiferous composition, of lignosuiphonate.
GB9313759A 1993-07-02 1993-07-02 Additives for cement compositions Withdrawn GB2279655A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9313759A GB2279655A (en) 1993-07-02 1993-07-02 Additives for cement compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9313759A GB2279655A (en) 1993-07-02 1993-07-02 Additives for cement compositions

Publications (2)

Publication Number Publication Date
GB9313759D0 GB9313759D0 (en) 1993-08-18
GB2279655A true GB2279655A (en) 1995-01-11

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1258464A1 (en) * 2001-05-10 2002-11-20 Wacker-Chemie GmbH Use of a powder composition as rheologic additive
WO2008068000A2 (en) * 2006-12-06 2008-06-12 Construction Research & Technology Gmbh Rheology modifying additive for cementitious compositions
EP2368863A1 (en) * 2010-03-22 2011-09-28 Sika Technology AG Additive for hydraulically setting systems with improved processing
RU2455249C1 (en) * 2011-01-12 2012-07-10 Федеральное государственное образовательное учреждение высшего профессионального образования "Петербургский государственный университет путей сообщения" Mortar

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2114985A (en) * 1982-02-17 1983-09-01 Grace W R & Co Multicomponent superplasticizer for cement
US5047087A (en) * 1986-04-03 1991-09-10 National Starch And Chemical Investment Holding Corporation Cementiferous composition and additives for use in such compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2114985A (en) * 1982-02-17 1983-09-01 Grace W R & Co Multicomponent superplasticizer for cement
US5047087A (en) * 1986-04-03 1991-09-10 National Starch And Chemical Investment Holding Corporation Cementiferous composition and additives for use in such compositions

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1258464A1 (en) * 2001-05-10 2002-11-20 Wacker-Chemie GmbH Use of a powder composition as rheologic additive
WO2008068000A2 (en) * 2006-12-06 2008-06-12 Construction Research & Technology Gmbh Rheology modifying additive for cementitious compositions
WO2008068000A3 (en) * 2006-12-06 2009-02-26 Constr Res & Tech Gmbh Rheology modifying additive for cementitious compositions
US8394191B2 (en) 2006-12-06 2013-03-12 Construction Research & Technology Gmbh Rheology modifying additive for cementitious compositions
EP2368863A1 (en) * 2010-03-22 2011-09-28 Sika Technology AG Additive for hydraulically setting systems with improved processing
WO2011117178A1 (en) * 2010-03-22 2011-09-29 Sika Technology Ag Additive for hydraulically setting systems having improved processability
AU2011231754B2 (en) * 2010-03-22 2014-11-20 Sika Technology Ag Additive for hydraulically setting systems having improved processability
US10040722B2 (en) 2010-03-22 2018-08-07 Sika Technology Ag Additive for hydraulically setting systems with improved processing
RU2455249C1 (en) * 2011-01-12 2012-07-10 Федеральное государственное образовательное учреждение высшего профессионального образования "Петербургский государственный университет путей сообщения" Mortar

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Publication number Publication date
GB9313759D0 (en) 1993-08-18

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