WO2008101538A1 - Preparation de guar de methyle - Google Patents

Preparation de guar de methyle Download PDF

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Publication number
WO2008101538A1
WO2008101538A1 PCT/EP2007/010705 EP2007010705W WO2008101538A1 WO 2008101538 A1 WO2008101538 A1 WO 2008101538A1 EP 2007010705 W EP2007010705 W EP 2007010705W WO 2008101538 A1 WO2008101538 A1 WO 2008101538A1
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WO
WIPO (PCT)
Prior art keywords
guar
methyl
ether
water
ethers
Prior art date
Application number
PCT/EP2007/010705
Other languages
English (en)
Inventor
Roland Bayer
Karsten BÖHME
Hans-Jürgen Juhl
Matthias Knarr
Peter Wolbers
Original Assignee
Dow Global Technologies Inc.
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 Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Publication of WO2008101538A1 publication Critical patent/WO2008101538A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/38—Polysaccharides or derivatives thereof
    • C04B24/383—Cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof

Definitions

  • the present invention relates to the preparation of methyl guar and the use in building materials.
  • DE-A 3 602 151 discloses the synthesis and the use of various methylated guar derivatives, such as methyl guar (MG), hydroxypropyl guar (HPG), methylhydroxy- propyl guar (MHPG), hydroxyethyl guar (HEG), methylhydroxyethyl guar (MHEG), in gypsum-based render materials as water retention agents.
  • MG methyl guar
  • HPG hydroxypropyl guar
  • MHPG methylhydroxy- propyl guar
  • HEG hydroxyethyl guar
  • MHEG methylhydroxyethyl guar
  • methyl guar derivatives or mixed ethers thereof having a degree of methyl substitution of from 1.0 to 2.0 which are obtained by solvent-free etherification of guar, have a comparatively high water retentivity in gypsum- and cement-bound systems.
  • the present invention therefore relates to a process for the preparation of methyl guar ethers or methyl guar mixed ethers, in which guar is methylated and, if appropriate, alkylated and/or hydroxyalkylated in the absence of a solvent so that a degree of substitution (DS), based on the methyl groups, of from 1.0 to 2.0 results.
  • DS degree of substitution
  • Methyl halides or dimethyl sulfate are typically used for the methylation.
  • Mixed ethers of guar having methyl ether groups and further alkyl ether groups and/or hydroxyalkyl ether groups are guar derivatives as may be obtained by methylation and prior, simultaneous or subsequent alkylation and/or hydroxyalkylation.
  • alkyl halides such as ethyl chloride
  • alkylene oxides such as ethylene oxide or propylene oxide
  • bases such as sodium hydroxide
  • the oxygen is expediently removed from the reaction mixture by evacuation and flushing with nitrogen.
  • the degree of substitution (DS) of the product is controlled via the amount of base used, preferably sodium hydroxide.
  • base used preferably sodium hydroxide.
  • NaOH can be used as aqueous solution or in solid form (NaOH prills or scales).
  • the reaction is expediently carried out in an optionally stirred autoclave or pressure reactor.
  • the metering of the reactants can be effected in any desired sequence, over any desired period, completely or divided into a plurality of steps.
  • the reaction temperatures are typically from 45°C to 140 0 C, preferably from 50 0 C to 100°C, particularly preferably from 80°C to 95 0 C.
  • reaction times until achieving the desired degree of etherification are typically from 10 to 250 min, preferably from 15 to 60 min.
  • the guar ethers are suspended in an inert suspending medium, e.g. acetone or toluene, and neutralized with an acid.
  • an inert suspending medium e.g. acetone or toluene
  • the salt-containing products are purified by washing with acidic water.
  • the purified guar ethers are then neutralized in an inert suspending medium, dried and, if appropriate, milled.
  • the methyl guar ethers or the corresponding mixed ethers have a degree of substitution (DS), based on the methylation, of preferably from 1.0 to 2.0, particularly preferably from 1.0 to 1.5.
  • DS degree of substitution
  • the methyl guar ethers or the corresponding mixed ethers typically have a degree of substitution (DS), based on the hydroxyalkylation, of from 0.01 to 5, preferably from 0.05 to 3, particularly preferably from 0.1 to 2.5.
  • DS degree of substitution
  • the guar ether is reacted with hot, concentrated hydriodic acid (Zeisel cleavage) and the resulting alkyl iodides and alkylenes are gas chromatically separated and analyzed.
  • the guar ethers of the abovementioned type which are used according to the invention preferably have viscosities at 20 0 C, measured using a rotational viscometer (Thermo Haake) at a shear rate of 2.55 s "1 with a 2% by weight aqueous solution, of from 1000 to 80 000 mPa-s, particularly preferably from 1500 to 60 000 mPa-s, very particularly preferably from 10 000 to 50 000 mPa-s.
  • a further subject comprises the methyl guar ethers or methyl guar mixed ethers obtainable by the process according to the invention and building material compositions which contain them. - A -
  • the methyl guar derivatives according to the invention exhibit pronounced water retentivity.
  • building material compositions such as mineral- or dispersion-bound systems, such as hand and machine renders, for example based on gypsum, slaked lime or cement, dispersion-bound renders, mortars, cement- and dispersion-bound tile adhesives, air-placed concrete masses, floor leveling masses, cement extrudates and lime-sandstone extrudates, cement-, gypsum- and dispersion-bound joint fillers and filling masses.
  • building material compositions such as mineral- or dispersion-bound systems, such as hand and machine renders, for example based on gypsum, slaked lime or cement, dispersion-bound renders, mortars, cement- and dispersion-bound tile adhesives, air-placed concrete masses, floor leveling masses, cement extrudates and lime-sandstone extrudates, cement-, gypsum- and dispersion-bound joint fillers and filling masses.
  • the above- described methyl guar ethers or mixed ethers essential to the invention are present in amounts of from 0.001 to 20% by weight, preferably from 0.001 to 5% by weight. based on the total dry mass.
  • exclusively guar ethers of the abovementioned type having methyl ether groups and, if appropriate, alkyl ether groups and/or hydroxyalkyl ether groups are present in the guar ether component in the building material compositions according to the invention.
  • the building material compositions may also contain cellulose derivatives, such as methylcelluloses, ethylcelluloses, hydroxypropylmethylcelluloses, hydroxyethylmethylcelluloses, hydroxypropylcelluloses and hydroxyethylcelluloses.
  • cellulose derivatives such as methylcelluloses, ethylcelluloses, hydroxypropylmethylcelluloses, hydroxyethylmethylcelluloses, hydroxypropylcelluloses and hydroxyethylcelluloses.
  • the building material compositions may contain additives and/or modifiers. These may be, for example, hydrocolloids, plastic dispersion powders, defoamer, swelling agents, fillers, lightweight additives, polyacrylates, polyacrylamides, hydrophobizing agents, water repellents, air-pore formers, synthetic thickeners, dispersants, liquefiers, plasticizers, retardants, accelerators or stabilizers. Furthermore, fillers, such as quartz sand, dolomite, lime-sandstone, calcium sulfate dihydrate, are suitable as additives and/or modifiers. The invention furthermore relates to moldings and structures obtainable using the building material compositions according to the invention.
  • additives and/or modifiers may be, for example, hydrocolloids, plastic dispersion powders, defoamer, swelling agents, fillers, lightweight additives, polyacrylates, polyacrylamides, hydrophobizing agents, water repellents, air-pore formers, synthetic thickeners, dispersants, liquefiers,
  • the viscosities were measured using a Haake rotational viscometer (Thermo Haake) at a shear rate of 2.55 s "1 and at a temperature of 20°C with DIN measuring bodies in pure aqueous solution.
  • guar flour 1 mol was suspended in 800 g of toluene in a 5 I stirred autoclave and rendered inert 3 times by evacuating and aerating with nitrogen gas. Thereafter, 0.75 mol of a 50% by weight sodium hydroxide solution was added over a period of 5 min and stirring was effected for a further 25 minutes at a temperature of 25°C. After evacuating and aerating with nitrogen gas a further 3 times, 1 mol of methyl chloride was added to the autoclave, heated to 9O 0 C in the course of 30 min and allowed to react at this temperature for 240 min.
  • the guar ether was removed, adjusted to a pH of 4 in toluene with acetic acid and temporarily crosslinked in the presence of 12.8 g of a 40% by weight aqueous glyoxal solution. After washing with water (pH 4) the purified guar ether was neutralized in toluene with 10% by weight NaOH, dried and milled.
  • the guar ether present as a white powder had a DS, based on the methyl ether groups, of 0.5 and a viscosity of a 2% by weight solution in water (V2 viscosity) of 20 280 mPa-s at 20 0 C.
  • V2 viscosity 20 280 mPa-s at 20 0 C.
  • guar flour 1 mol was suspended in 800 g of toluene in a 5 I stirred autoclave and rendered inert 3 times by evacuating and aerating with nitrogen gas. Thereafter, 1.66 mol of a 50% by weight sodium hydroxide solution were added over a period of 5 min and stirring was effected for a further 25 minutes at a temperature of 25°C. After evacuating and aerating with nitrogen gas a further 3 times, 2.2 mol of methyl chloride was added to the autoclave, heated to 9O 0 C in the course of 30 min and allowed to react at this temperature for 240 min.
  • the guar ether was removed, adjusted to a pH of 4 in toluene with acetic acid and temporarily crosslinked in the presence of 12.8 g of a 40% by weight aqueous glyoxal solution. After washing with water (pH 4) the purified guar ether was neutralized in toluene with 10% by weight NaOH, dried and milled.
  • the guar ether present as a white powder had a DS, based on the methyl ether groups, of 1.22 and a viscosity of a 2% by weight solution in water (V2 viscosity) of 13 880 mPa s at 20 0 C.
  • guar flour 1 mol was suspended in 800 g of toluene in a 5 I stirred autoclave and rendered inert 3 times by evacuating and aerating with nitrogen gas. Thereafter, 2.33 mol of a 50% by weight sodium hydroxide solution were added over a period of 5 min and stirring was effected for a further 25 minutes at a temperature of 25°C. After evacuating and aerating with nitrogen gas a further 3 times, 3.03 mol of methyl chloride was added to the autoclave, heated to 90 0 C in the course of 30 min and allowed to react at this temperature for 240 min.
  • the guar ether was removed, adjusted to a pH of 4 in toluene with acetic acid and temporarily crosslinked in the presence of 12.8 g of a 40% by weight aqueous glyoxal solution. After washing with water (pH 4) the purified guar ether was neutralized in toluene with 10% by weight NaOH, dried and milled.
  • the guar ether present as a white powder had a DS, based on the methyl ether groups, of 1.54 and a viscosity of a 2% by weight solution in water (V2 viscosity) of 13 38O mPa-S at 20 0 C.
  • guar flour 1 mol was rendered inert in a 5 I stirred autoclave by evacuating and aerating with nitrogen gas 3 times. Thereafter, 0.65 mol of a 50% by weight sodium hydroxide solution and 5.82 mol of methyl chloride were added to the autoclave and stirred for 30 minutes at a temperature of 25°C. Heating was effected in the course of 30 min to 9O 0 C and stirring was effected at this temperature for 240 min. After removal of unreacted methyl chloride, the guar ether was removed, adjusted to a pH of 5 in acetone with acetic acid and temporarily crosslinked in the presence of 9.1 g of a 40% by weight aqueous glyoxal solution.
  • the purified guar ether was neutralized in acetone with 10% by weight NaOH, dried and milled.
  • the guar ether present as white powder had a DS 1 based on the methyl ether groups, of 0.48 and a viscosity of a 2% by weight solution in water (V2 viscosity), of 33 250 mPa-s at 20 0 C.
  • guar flour 1 mol was rendered inert in a 5 I stirred autoclave 3 times by evacuating and aerating with nitrogen gas. Thereafter, 1.88 mol of a 50% by weight sodium hydroxide solution and 5.82 mol of methyl chloride were added to the autoclave over a period of 5 min and stirred for a further 25 minutes at a temperature of 25°C. Heating was effected in the course of 30 min to 80 0 C and reaction was allowed to take place at this temperature for 240 min.
  • the guar ether was removed, adjusted to a pH of 5 in acetone with acetic acid and temporarily crosslinked in the presence of 11.4 g of a 40% by weight aqueous glyoxal solution. After washing with water (pH 4), the purified guar ether was neutralized in acetone with 10% by weight NaOH, dried and milled.
  • the guar ether present as a white powder had a DS, based on the methyl ether groups, of 1.23 and a viscosity of a 2% by weight solution in water (V2 viscosity) of 30 980 mPa-s at 20 0 C.
  • guar flour 1.5 mol was rendered inert in a 5 I stirred autoclave 3 times by evacuating and aerating with nitrogen gas. Thereafter, 3.0 mol of a 50% by weight sodium hydroxide solution and 5.82 mol of methyl chloride were added to the autoclave over a period of 5 min and stirred for a further 25 minutes at a temperature of 25°C. Heating was effected in the course of 30 min to 80 0 C and reaction was allowed to take place at a temperature of 80 0 C for 30 min.
  • the guar ether was removed, adjusted to a pH of 4 in acetone with acetic acid and temporarily crosslinked in the presence of 20.4 g of a 40% by weight aqueous glyoxal solution. After washing with water (pH 4), the purified guar ether was neutralized in acetone with 10% by weight
  • the guar ether present as a white powder had a DS, based on the methyl ether groups, of 1.38 and a viscosity of a 2% by weight solution in water (V2 viscosity) of 31 580 mPa-s at 20°C.
  • the slump is the diameter of a cake of a water/render mixture (gypsum or cement) in mm which forms after demolding and shocking of the mixture by vertical impacts.
  • the commercially available unmodified gypsum machine plaster was mixed with 0.21% of the corresponding guar derivative or a commercially available unmodified lime-cement render with 0.08% of the corresponding guar derivative as an additive and stirred in a mortar mixer according to DIN 1164 Sheet 7 with the corresponding amount of tap water at 20 0 C.
  • the corresponding amount of water was initially introduced into the mixer and the gypsum plaster was sprinkled in within 15 seconds with the stirrer running at speed 1 and mixed for a further 20 seconds at speed 2.
  • the lime-cement render a corresponding amount of water was initially introduced into the mixer and the lime- cement render was sprinkled in within 15 seconds with the stirrer running at speed 1 and mixed for a further 30 seconds at speed 1.
  • the diameter of the plaster or render was determined using a caliper gauge.
  • the corresponding amount of water was chosen so that a slump of 170 ⁇ 5 mm resulted for the gypsum plaster and a slump of 170 ⁇ 10 mm for the lime-cement render.
  • the resultant water/solid factor is calculated according to
  • the water retentivity of a mineral render is the proportion of water, expressed in percent, which remains in the render after capillary withdrawal of water by the absorptive substrate.
  • the render is brought into contact with a filter sheet for a specified time and the amount of water taken up by the filter paper is then determined.
  • the ring is filled with the corresponding amount of render, the projecting amount of render is scraped off with a spatula and the amount present in the ring is accurately determined by weighing.
  • the pulp board withdraws water from the render material, which is determined accurately by reweighing the moist cardboard.
  • the release paper serves only for enabling the render to be removed more easily from the board after a suction time of 5 or 30 minutes.
  • the water retentivity (WR) is defined as:
  • A water absorption of the pulp board and of the release paper in g
  • a high water retentivity means that the render does not dry out after application and the water required for setting is available to it for a sufficiently long time.
  • the water retentivity of the guar derivatives according to the invention which were used in the render application is substantially above that of the samples prepared in toluene.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne la préparation de guar de méthyle et son utilisation dans des matériaux de construction.
PCT/EP2007/010705 2007-02-23 2007-12-08 Preparation de guar de methyle WO2008101538A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007008842.8 2007-02-23
DE200710008842 DE102007008842A1 (de) 2007-02-23 2007-02-23 Herstellung von Methylguar

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WO2008101538A1 true WO2008101538A1 (fr) 2008-08-28

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DE (1) DE102007008842A1 (fr)
TW (1) TW200846373A (fr)
WO (1) WO2008101538A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8946305B2 (en) 2011-12-22 2015-02-03 Industrial Technology Research Institute Method for crosslinking a colloid, and crosslinked colloid therefrom

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912713A (en) * 1973-08-29 1975-10-14 Scholten Honig Research Nv Guar gum derivatives and process for preparation
US4169945A (en) * 1978-01-05 1979-10-02 Celanese Corporation Process for production of polygalactomannan ethers
EP0186164A2 (fr) * 1984-12-27 1986-07-02 HENKEL CORPORATION (a Delaware corp.) Application de résines éthérifiées de polygalactomannane comme stabilisants pour suspensions charbonneuses
EP0209122A1 (fr) * 1985-07-18 1987-01-21 HENKEL CORPORATION (a Delaware corp.) Mélange charbon-eau comprenant un agent tensioactif d'oxyde de polyalkylène et du polygalactomannane
EP0235513A2 (fr) * 1986-01-24 1987-09-09 Henkel Kommanditgesellschaft auf Aktien Mélange alcalin de plâtre avec des dérivés de guar
EP0277499A1 (fr) * 1987-01-21 1988-08-10 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'éthers ou de mélanges d'éthers de guar à partir de particules de guar
EP0708114A1 (fr) * 1994-10-17 1996-04-24 Aqualon Company Ethylguar, procédé de préparation et son utilisation
WO2007051723A2 (fr) * 2005-10-31 2007-05-10 Lamberti Spa Additifs bases sur du guar de methyle utilises dans des compositions de construction

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912713A (en) * 1973-08-29 1975-10-14 Scholten Honig Research Nv Guar gum derivatives and process for preparation
US4169945A (en) * 1978-01-05 1979-10-02 Celanese Corporation Process for production of polygalactomannan ethers
EP0186164A2 (fr) * 1984-12-27 1986-07-02 HENKEL CORPORATION (a Delaware corp.) Application de résines éthérifiées de polygalactomannane comme stabilisants pour suspensions charbonneuses
EP0209122A1 (fr) * 1985-07-18 1987-01-21 HENKEL CORPORATION (a Delaware corp.) Mélange charbon-eau comprenant un agent tensioactif d'oxyde de polyalkylène et du polygalactomannane
EP0235513A2 (fr) * 1986-01-24 1987-09-09 Henkel Kommanditgesellschaft auf Aktien Mélange alcalin de plâtre avec des dérivés de guar
EP0277499A1 (fr) * 1987-01-21 1988-08-10 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'éthers ou de mélanges d'éthers de guar à partir de particules de guar
EP0708114A1 (fr) * 1994-10-17 1996-04-24 Aqualon Company Ethylguar, procédé de préparation et son utilisation
WO2007051723A2 (fr) * 2005-10-31 2007-05-10 Lamberti Spa Additifs bases sur du guar de methyle utilises dans des compositions de construction

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RISICA ET AL: "Guar gum methyl ethers. Part I. Synthesis and macromolecular characterization", 12 December 2005, POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, PAGE(S) 12247-12255, ISSN: 0032-3861, XP005215884 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8946305B2 (en) 2011-12-22 2015-02-03 Industrial Technology Research Institute Method for crosslinking a colloid, and crosslinked colloid therefrom

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TW200846373A (en) 2008-12-01
DE102007008842A1 (de) 2008-08-28

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