US20020193279A1 - Thixotropic dispersions of polysuccinimide and their use - Google Patents

Thixotropic dispersions of polysuccinimide and their use Download PDF

Info

Publication number
US20020193279A1
US20020193279A1 US10/146,833 US14683302A US2002193279A1 US 20020193279 A1 US20020193279 A1 US 20020193279A1 US 14683302 A US14683302 A US 14683302A US 2002193279 A1 US2002193279 A1 US 2002193279A1
Authority
US
United States
Prior art keywords
dispersion
polysuccinimide
psi
thixotropic
dispersions
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.)
Abandoned
Application number
US10/146,833
Other languages
English (en)
Inventor
Thomas Klein
Joachim Voss
Holger Schmidt
Fred Ebert
Harry-Gunter Muller
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.)
Bayer AG
Original Assignee
Individual
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 Individual filed Critical Individual
Assigned to BAYER AKTIENGESELLSCHAFT reassignment BAYER AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EBERT, FRED, MUELLER, HARRY-GUENTER, VOSS, JOACHIM, KLEIN, THOMAS, SCHMIDT, HOLGER
Publication of US20020193279A1 publication Critical patent/US20020193279A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1092—Polysuccinimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers

Definitions

  • the present invention relates to stable thixotropic polysuccinimide (PSI) dispersions, known as slurries, and to their use as additives for improving the flow properties of concrete, in oil wells, in acidic gel cleaners, and in drainage systems of tunnel constructions.
  • PSI polysuccinimide
  • Stable in the sense of the present invention means stable against separation of liquid and solid compounds.
  • polyaspartic acids are highly effective in the breakup or reformation of deposits, such as those of calcium carbonate.
  • the effect is founded firstly on the pH in the immediate vicinity of the opening succinimides in the PSI, secondly, following neutralization of the polyaspartic acid, on the dispersing action of the polyaspartate anion.
  • polyaspartic acid in an acidic environment is hindered, however, by its instability under these conditions.
  • Polyaspartic acid is subject to acidic hydrolysis to monomeric aspartic acid, especially under a thermal load (investigations by Bayer AG, brochure “PASP Na-Salz”—polyaspartic acid sodium salt; a new, biodegradable dispersant, Edition 3.99, Order No.: CH 201201). It was possible to show that a 1% strength polyaspartic acid undergoes 61% hydrolysis after 24 h at a pH of 4, 77% hydrolysis at a pH of 2, which particularly in the case of oil wells is disadvantageous.
  • Cleaners very often contain viscosity-increasing substances. Examples of cleaners are given in U.S. Pat. No. 6,083,890 with xanthan as thickener, in U.S. Pat. No. 6,004,916 with ammonium EDTA as complexing agent and a solvent, and also nonionic surfactants as dispersion media, and in U.S. Pat. No. 5,554,320 with phosphoric acid and paraffinsulfonate, fatty alcohol-EP/PO copolymer as surfactant.
  • JP-A 8 169 741 describes the use of powderous polysuccinimide for improving the flow behavior of mortar mixtures with Portland cement. Incorporation in powder form, however, is typical, since uniform distribution within the cement mortar is achieved only by prolonged mixing. Uniform distribution is absolutely necessary, since inhomogeneities lead to problems with the ultimate hardness of the cement. It would be advantageous to provide PSI as a paste or dispersion in water, in which the wetting of the polysuccinimide by water had already taken place and which would therefore prevent the lumping that occurs in the course of stirred incorporation.
  • the object was therefore to find thixotropic formulations of PSI with water which meet all of these requirements as regards stability and liquefiability.
  • thixotropic dispersions of PSI with water according to the present invention exhibit all of these properties.
  • the invention relates to a stable thixotropic dispersion comprising polysuccinimide in a protic solvent.
  • the invention also relates to a process for preparing a thixotropic polysuccinimide dispersion comprising: (a) introducing polysuccinimide and/or its copolymers to a vessel, (b) adding a protic solvent and surfactant to the vessel and mixing, thereby forming a mixture, (c) thoroughly mixing the mixture, thereby forming a homogeneous dispersion, and (d) solidifying the homogeneous dispersion.
  • the present invention accordingly provides thixotropic dispersions of polysuccinimide and protic solvents, preferably with water, with particular preference deionized water, which further comprise a hydrocolloid, preferably a surfactant, with particular preference an anionic or nonionic surfactant.
  • PSI in the fine-particled state required for the thixotropic dispersions of the invention may be prepared in accordance with the processes of DE-A 19 706 901 or EP-A 0 786 487, incorporated herein by reference in their entirety.
  • the thixotropic PSI dispersions of the invention contain from about 10 to about 90% by weight of PSI, preferably from about 30 to about 70% by weight of PSI, with particular preference from about 40 to about 60% by weight of PSI.
  • the thixotropic PSI dispersions of the invention are prepared by intensively stirring a finely particulate polysuccinimide having a typical particle size in the maximum of a few hundred ⁇ m.
  • a PSI having a particle diameter of from about 10 to about 250 ⁇ m, preferably from about 10 to about 150 ⁇ m, with particular preference from about 10 to about 100 ⁇ m, and, with very particular preference, of from about 10 to about 70 ⁇ m in the maximum of the distribution is used.
  • the large surface area is advantageous for the rapid establishment of equilibrium.
  • the thixotropic PSI dispersions of the invention contain from about 0.01 to about 20% by weight of surfactants, preferably from about 1 to about 10% by weight of surfactants, with particular preference from about 1 to about 5% by weight of surfactants.
  • the function of the surfactant is to disperse the PSI as finely as possible.
  • nonionic and anionic surfactants are suitable in principle; owing to the positive charge, cationic surfactants may lead to instances of flocculation of electroneutral aggregates with the polyaspartate anion.
  • Preferred surfactants in the context of the present invention are nonionic surfactants, with particular preference fatty alcohol ethoxylates, with very particular preference C 14 -C 16 fatty alcohols having a degree of ethoxylation of 20-40.
  • the thixotropic PSI dispersions of the invention may comprise thickeners, with particular preference biodegradable thickeners.
  • biodegradable thickeners are added to the thixotropic PSI dispersions.
  • preferred thickeners used are cellulose ethers.
  • a particularly preferred thickener used is methylcellulose.
  • the PSI dispersions of the invention are obtainable by dispersing the PSI in a protic solvent, preferably water, especially deionized water.
  • the dispersions of the invention are prepared by first introducing PSI and/or its copolymers, adding the water and homogenizing the water thoroughly using an Ultra-turrax—or a similar stirring apparatus suitable for the present purpose. Thereafter, the surfactant is added and thorough mixing with the Ultra-turrax is repeated. Finally, a homogeneous dispersion is obtained which soon solidifies after the stirring operation.
  • PSI represents an alternative to polyaspartic acid because it can be converted into a fine, stable dispersion which does not sediment and which, through an increase in viscosity, substantially suppresses diffusion and thus hydrolysis in water.
  • an inventive PSI dispersion is able to be liquefied by means of shear forces, so making available polyaspartic acid in the manner of a sustained release effect.
  • the amount of polyaspartic acid present in equilibrium with polysuccinimide under these conditions is available in order, for example, to break up calcium carbonate encrustations.
  • the polyaspartic acid then removed from the system by neutralization can be reformed by hydrolysis, so that there is always sufficient (although low) concentrations of free polyaspartic acid available.
  • Fine stable PSI dispersions of the invention are also suitable for use as acidic gel cleaners, such as, for instance, in the sanitary segment for dissolving lime deposits.
  • a gel cleaner flows along the surface to be cleaned, but thickens when there are no shear forces and so remains adhering to the surface.
  • the contact time especially in the case of vertical surfaces, remains greatly increased, as does, consequently, the cleaning effect when thixotropic PSI dispersions according to the present invention are used.
  • the thixotropic PSI dispersions of the invention exhibit the desired viscosity behavior, the stability needed for the above-mentioned applications, and also liquefiability.
  • the dispersions are stable at least 300 days at a temperature that is less than about 20° C., or from at least 200 days at a temperature that is less than about 25° C., or from at least 150 days to about 200 days at a temperature ranging from about 25° C. to about 30° C.
  • the thixotropic PSI dispersions of the present invention permit the cleaning of sanitary installations or of scratch-sensitive surfaces such as, for example, plastics, bronze, brass, silver, lead crystal or glass ceramic hobs.
  • the present invention therefore also relates to cements or concretes and also gel cleaners which comprise a flow-property-improving fraction of thixotropic PSI dispersions.
  • FIGS. 1 and 2 show by way of example two measurements of a PSI slurry of 47.5% by weight PSI, 47.5% by weight water and 5% by weight Disponil®.
  • Disponil® is a surfactant from Henkel AG
  • FIGS. 3 and 4 show by way of example two measurements of a PSI slurry of 48.5% by weight PSI, 48.5% by weight water and 3% by weight Dehydol®.
  • Dehydol® is a surfactant of Henkel AG.
  • Water-based PSI slurries may be prepared using a thickener even with relatively small amounts of active substance, as the following example shows.
  • a formulation according to Example 1 was capable of dissolving calcium carbonate, as the following example shows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Colloid Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Detergent Compositions (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
US10/146,833 2001-05-22 2002-05-16 Thixotropic dispersions of polysuccinimide and their use Abandoned US20020193279A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10124903A DE10124903A1 (de) 2001-05-22 2001-05-22 Thixotrope Dispersionen von Polysuccinimid und deren Anwendung
DE10124903.9 2001-05-22

Publications (1)

Publication Number Publication Date
US20020193279A1 true US20020193279A1 (en) 2002-12-19

Family

ID=7685710

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/146,833 Abandoned US20020193279A1 (en) 2001-05-22 2002-05-16 Thixotropic dispersions of polysuccinimide and their use
US10/152,437 Expired - Fee Related US6861398B2 (en) 2001-05-22 2002-05-21 Thixotropic dispersions of polysuccinimide and their use

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/152,437 Expired - Fee Related US6861398B2 (en) 2001-05-22 2002-05-21 Thixotropic dispersions of polysuccinimide and their use

Country Status (6)

Country Link
US (2) US20020193279A1 (de)
EP (1) EP1260539B1 (de)
AT (1) ATE337356T1 (de)
CA (1) CA2387001C (de)
DE (2) DE10124903A1 (de)
NO (1) NO328173B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6861398B2 (en) * 2001-05-22 2005-03-01 Bayer Aktiengesellschaft Thixotropic dispersions of polysuccinimide and their use

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10327682A1 (de) * 2003-06-20 2005-01-05 Bayer Chemicals Ag Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
US7744742B2 (en) * 2007-11-28 2010-06-29 Chevron U.S.A. Inc. Integration of molecular redistribution and hydroisomerization processes for the production of paraffinic base oil

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266237A (en) * 1992-07-31 1993-11-30 Rohm And Haas Company Enhancing detergent performance with polysuccinimide
US5554320A (en) 1993-11-22 1996-09-10 Yianakopoulos; Georges Liquid cleaning compositions
JPH08169741A (ja) 1994-12-16 1996-07-02 Mitsui Toatsu Chem Inc 徐放性セメント用混和剤
US6054553A (en) * 1996-01-29 2000-04-25 Bayer Ag Process for the preparation of polymers having recurring agents
DE19603053A1 (de) 1996-01-29 1997-07-31 Bayer Ag Verfahren zur Herstellung von Polymeren mit wiederkehrenden Succinyl-Einheiten
US5814591A (en) 1996-04-12 1998-09-29 The Clorox Company Hard surface cleaner with enhanced soil removal
ZA974982B (en) 1996-06-06 1998-01-23 Monsanto Co Acidic cleaning compositions containing xanthan gum.
DE19706901A1 (de) 1997-02-21 1998-08-27 Bayer Ag Verfahren zur Durchführung von Polykondensationsreaktionen
EP0884344A3 (de) * 1997-06-11 1999-11-17 Th. Goldschmidt AG Milde tensidhaltige Zubereitungen mit copolymeren Polyasparaginsäurederivaten für kosmetische oder Reinigungszwecke
DE19908564A1 (de) * 1998-03-12 1999-09-16 Dorus Klebetechnik Gmbh & Co K Reinigungsmittel für PVC-Oberflächen
DE19842054A1 (de) * 1998-09-15 2000-03-16 Bayer Ag Verwendung von wasserlöslichen polymeren Polycarboxylaten in Reinigerformulierungen mit abrasiver Wirkung
US6419016B1 (en) * 2000-09-29 2002-07-16 Halliburton Energy Services, Inc. Methods of cementing in subterranean zones
DE10124903A1 (de) * 2001-05-22 2002-11-28 Bayer Ag Thixotrope Dispersionen von Polysuccinimid und deren Anwendung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6861398B2 (en) * 2001-05-22 2005-03-01 Bayer Aktiengesellschaft Thixotropic dispersions of polysuccinimide and their use

Also Published As

Publication number Publication date
NO20022392L (no) 2002-11-25
EP1260539B1 (de) 2006-08-23
CA2387001A1 (en) 2002-11-22
DE10124903A1 (de) 2002-11-28
EP1260539A1 (de) 2002-11-27
ATE337356T1 (de) 2006-09-15
NO20022392D0 (no) 2002-05-21
US20030060391A1 (en) 2003-03-27
US6861398B2 (en) 2005-03-01
DE50207899D1 (de) 2006-10-05
CA2387001C (en) 2009-06-30
NO328173B1 (no) 2009-12-28

Similar Documents

Publication Publication Date Title
JP2827152B2 (ja) 塵埃抑制方法
EA002733B1 (ru) Цементирующая композиция и ее применение для цементирования нефтяных скважин или подобных скважин
US20190330109A1 (en) Preparation of water-reducing composition, water-reducing composition and hydraulic composition
MXPA02005725A (es) Agentes de control de aire, solubles en agua para composiciones de cemento.
US6861398B2 (en) Thixotropic dispersions of polysuccinimide and their use
US5376173A (en) Segregation reducing agent for hydraulic composition and hydraulic composition
JPH07100606B2 (ja) ミクロシリカスラリ−及びその製造方法
CA2397129C (en) Stable aqueous polymeric superplasticizer solutions and concrete compositions containing the same
CN116769453A (zh) 一种基于两步法制备的盾构用分散型泡沫剂、其制备方法和应用
JP4627153B2 (ja) 懸濁型地盤改良材及びその製造方法
JPS6011255A (ja) セメント添加剤
US6100319A (en) Process for improving the plasticity of ceramic composition and for reversing this effect
JP5153987B2 (ja) 懸濁型地盤改良材の調製法
JPS5992961A (ja) セメント固定遅延剤組成物
JP3502595B2 (ja) 地盤改良工法用添加剤
JP3963513B2 (ja) ポリアルキレンオキシド水性分散液およびその製造方法
JP4190877B2 (ja) 硫酸カルシウムスラリー組成物
JPS60258139A (ja) 金属石けんの水分散体
CN1128166C (zh) 丙烯酰胺－双丙酮丙烯酰胺共聚物的制备方法
AU2005202532B2 (en) Water-Soluble Air-Controlling Agents for Cementitious Compositions
JP2001130937A (ja) セメント添加剤およびこれを含むセメント組成物
JPH04175253A (ja) セメント組成物の流動性低下防止剤
TW201945314A (zh) 減水劑組成物之製造方法、減水劑組成物及水硬性組成物
JPS605052A (ja) セメント分散剤
Kwaambwa Short communication Stability and phase separation behaviour of systems of particles in a medium with added polymer

Legal Events

Date Code Title Description
AS Assignment

Owner name: BAYER AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KLEIN, THOMAS;VOSS, JOACHIM;SCHMIDT, HOLGER;AND OTHERS;REEL/FRAME:012915/0395;SIGNING DATES FROM 20020507 TO 20020508

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION