WO1996027618A1 - Verfahren zur herstellung von neutralisierten polycarboxylaten auf polysaccharid-basis - Google Patents
Verfahren zur herstellung von neutralisierten polycarboxylaten auf polysaccharid-basis Download PDFInfo
- Publication number
- WO1996027618A1 WO1996027618A1 PCT/EP1996/000791 EP9600791W WO9627618A1 WO 1996027618 A1 WO1996027618 A1 WO 1996027618A1 EP 9600791 W EP9600791 W EP 9600791W WO 9627618 A1 WO9627618 A1 WO 9627618A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid
- oxidation
- polysaccharides
- neutralizing agent
- nitrogen dioxide
- Prior art date
Links
- 150000004676 glycans Chemical class 0.000 title claims abstract description 33
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 33
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 32
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 27
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 22
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- 125000000075 primary alcohol group Chemical group 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 49
- 230000003647 oxidation Effects 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229920002472 Starch Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 12
- 235000019698 starch Nutrition 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001272 nitrous oxide Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 229920001592 potato starch Polymers 0.000 claims description 3
- 239000013042 solid detergent Substances 0.000 claims description 3
- 229920002261 Corn starch Polymers 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229920002678 cellulose Polymers 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 5
- 229960001730 nitrous oxide Drugs 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- DKSMCEUSSQTGBK-UHFFFAOYSA-M bromite Chemical compound [O-]Br=O DKSMCEUSSQTGBK-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- ACKFDYCQCBEDNU-UHFFFAOYSA-J lead(2+);tetraacetate Chemical compound [Pb+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ACKFDYCQCBEDNU-UHFFFAOYSA-J 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical class [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 230000000803 paradoxical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
Definitions
- the invention relates to a simplified process for the production of polycarboxylates in their salt form by selective oxidation of polysaccharides with gaseous nitrogen dioxide and dry neutralization of the oxidation product obtained.
- oxidizing agents are used for the oxidation of polysaccharides, in particular polyglucosans composed exclusively of glucose.
- examples include (air) oxygen, hydrogen peroxide, sodium hypochlorite or bromite, periodic acid or periodates, lead (IV) acetate, nitrogen dioxide and cerium (IV) salts.
- These oxidizing agents react very differently with the anhydroglucose units, cf. For example, the formula pictures in Houben-Weyl loc. cit., page 2124.
- periodates or lead (IV) acetate cause a CC cleavage of the anhydroglucose rings; so-called 2,3-dialdehyde cellulose is obtained from cellulose and dialdehyde starch is obtained analogously from starch.
- 2,3-dialdehyde cellulose is obtained from cellulose
- dialdehyde starch is obtained analogously from starch.
- nitrogen dioxide acts on cellulose
- the oxidizing agent usually in equilibrium with di-nitrogen tetroxide
- gaseous or dissolved in an inert organic solvent can be used, cf. here also Houben-Weyl op. cit. page 2125 and the primary literature mentioned there in this context.
- a polysaccharide selectively oxidized to C5 is obtained in solid form.
- This sparingly water-soluble acid form is not well suited for direct use as a builder or builder component (cobuilder) in detergents or cleaning agents; it is generally preferred to use the oxidized polysaccharide in the form of a water-soluble salt, that is to say the neutralization product of the polycarboxylic acid obtained in the oxidation. So far, it has been suggested Perform neutralization with aqueous base.
- the invention is a process for the production of solid polycarboxylic acid salts from polysaccharides by oxidation with gaseous nitrogen dioxide / dinitrogen tetroxide with conversion of at least some of the primary alcohol groups of the polysaccharides into carboxyl groups and at least partial neutralization of the resulting Carboxylic acid groups, which is characterized in that the solid polycarboxylic acid is mixed with a solid neutralizing agent.
- the oxidation of the polysaccharide preceding the neutralization essential to the invention is preferably carried out as described in the German patent application P 44 26443.7.
- the reaction of the polysaccharide to be oxidized with nitrogen dioxide / dinitrogen tetroxide is carried out only so long that the desired degree of oxidation, that is to say the degree of conversion of the primary alcohol groups into carboxyl groups, only to a maximum of 90%, preferably to 60% to 85% and in particular 65% to 80% is achieved.
- the desired degree of oxidation is only fully achieved in the post-oxidation phase, that is to say when the nitrogen dioxide / dinitrogen tetroxide feed has ended and in comparison to the oxidation phase by at least 10 ° C., preferably 15 ° C. to 80 ° C. and in particular 20 ° C. to 50 ° C. ° C elevated temperature. Care should be taken to ensure that an increase in temperature does not exceed an upper limit of 160 ° C, since decomposition has been observed increasingly at higher temperatures.
- the oxidation reaction to be terminated before complete conversion is preferably carried out at temperatures from 30 ° C. to 70 ° C., in particular from 40 ° C. to 60 ° C.
- Oxygen alone or in a mixture with gas which is inert under the reaction conditions, can be present, the addition of which can take place once at the start of the reaction or several times, if desired continuously, during the reaction.
- the oxidation reaction can, as is known, be controlled via the oxygen metering, depending on the temperature or pressure.
- the addition of oxygen is preferably controlled so that the reaction temperature remains in the range from 30 ° C. to 70 ° C.
- Noble gases such as helium or argon and carbon dioxide, but in particular nitrogen, nitrogen monoxide and dinitrogen monoxide, but also any mixtures of such gases can be used as inert gases, ie gases which do not react under the desired process conditions.
- the oxygen content in the gas mixture is preferably in the range from 1% by volume to 30% by volume, in particular from 3% by volume to 10% by volume.
- a preferred embodiment of the method according to the invention includes the supply of oxygen by injecting air.
- a further preferred embodiment of the process is characterized in that a pressure of less than 10 bar, in particular from 2 bar to 6 bar, is set at the desired reaction temperature in the reaction system before the start of the oxidation reaction by pressing in an inert gas and then Oxygen or a mixture of oxygen is injected with said inert gas several times, if desired continuously.
- the addition of nitrogen dioxide / nitrous oxide can take place before or after the addition of oxygen or the start of the addition of oxygen. It may be necessary to heat the reaction vessel to the desired reaction temperature after the initial injection of the inert gas.
- the reaction temperature can generally be maintained without the need for external heating solely by adding the amount of oxygen.
- the oxidizing agent from the gas phase acts directly on the solid, as intensively mixed polysaccharide substrates as possible.
- Oxidation in a fluidized bed made of polysaccharide is preferred, the fluidizing agent of which is a gas containing nitrogen dioxide.
- Fluid bed should be understood - without being restricted to this type of production - to be the phenomenon that can be observed when fine-grained bulk material stored on horizontal, perforated floors is flowed through from below by gases, referred to as fluidizing agents.
- fluidizing agents In this context, reference is made to the work of D. Kunii and 0.
- a useful reactor for the oxidation is also the device disclosed in European patent EP 051 147 B1 (there FIG. 1), in which there is a fluidized bed through which gas flows in a cylinder in which a shaft equipped with stirring arms rotates. It is also possible to use a reactor with a multi-stage fluidized bed, as in Beränek / Rose / Winterstein, "Fundamentals of the Fluidized Bed technik ", Krauskopf-Verlag, 1975, page 72. With such a device, the continuous reaction is easily possible.
- the fluidizing agent can leave the reaction system after flowing through the polysaccharide and, according to the invention, is replaced by a fluidizing agent which does not contain nitrogen dioxide / nitrous oxide tetroxide before the desired degree of oscillation has been reached.
- This fluidizing agent is preferably an inert gas described above.
- the reaction time required until the addition of nitrogen dioxide / dinitrogen tetroxide has ended essentially depends on the desired degree of oxidation and the temperature.
- the following information can serve as a guideline: At a temperature of 50 ° C and normal pressure using 12 molar equivalents of nitrogen dioxide per hour, based on hydroxyl groups to be oxidized, 18% to 22% after 30 minutes, 60% to 70% after 60 minutes and after 1.5 hours, 85% to 95% of the primary alcohol groups are converted into carboxyl groups.
- polysaccharide used is largely uncritical for the oxidation process described above. The only prerequisites are that it contains carbohydrate units containing primary alcohol groups and is in a form which permits intensive mixing with the gaseous oxidizing agent and preferably the formation of a fluidized bed, in particular in powder form.
- Native polyglucans in particular starch and / or cellulose, but also other polysaccharides, for example polygalactoannans such as guar and carubin, are suitable.
- the polysaccharides can also be used in chemically or physically modified form, provided that they still contain oxidizable primary alcohol groups.
- starches of different provenance in particular potato starch, wheat starch, corn starch and / or tapioca starch, as are commercially available as conventional powders, are preferred. Because cellulose often has problems with the formation of a fiber due to its fibrous nature If fluidized bed is prepared, it is preferably used in the form of micropowder.
- the process according to the invention in particular using the polyglucans mentioned, is preferably carried out in its oxidation step over such a period that the oxidation product is at least .15 mol% of oxidized anhydroglucose units of the formula I in the statistical mean
- a process according to the invention gives polycarbucates based on polyglucan, which preferably contain at least 25 mol%, in particular at least 35 mol%, of the oxidized anhydroglucose units, in particular of the formula I, with a further advantage being no significant amounts of other oxidation - Follow-up products are available.
- the upper limit of the content of units according to formula I is 100 mol%, in particular approximately 95 mol%.
- the process according to the invention preferably produces polycarboxylates which have units of the formula I in the range from 70 mol% to 100 mol%, corresponding to a carboxyl group content of up to about 25% by weight.
- the polysaccharide to be oxidized tends to agglomerate and to form channels, which is feared in fluidized bed technology
- its flow behavior can be achieved by adding small amounts of, in particular, solid additives, for example magnesium oxide, calcium fluoride, calcium phosphate, finely divided zeolites or silica gel, in particular silicon dioxide sold under the name Aerosil ( R ) can be significantly improved.
- high effects become apparent when using low amounts of additive, preferably from 0.1% by weight to 5% by weight, in particular 0.25% by weight to 1% by weight, based in each case on the polysaccharide to be oxidized.
- the polysaccharide used preferably contains not more than 15% by weight, in particular not more than 10% by weight, of water.
- the carboxyl groups of the oxidation product are neutralized according to the invention by treatment with a basic reagent present in solid form, ie converted from the acid to the salt form.
- a basic reagent present in solid form, ie converted from the acid to the salt form.
- All common solid, in particular powdery bases are possible as neutralizing agents, in particular alkali metal hydroxide, alkali metal carbonate, basic alkali metal silicate and basic alkali metal alumosilicate and mixtures thereof. It is irrelevant whether the neutralizing agent is in anhydrous or water containing form.
- the preferred neutralizing agents include sodium hydroxide, sodium carbonate, dried basic water glasses and basic zeolites obtained without the usual washing step, such as zeolite Na-A, X and / or P.
- the neutralizing agent is preferably used in such amounts that all carboxyl groups of the oxidation product are converted into the salt form.
- the neutralization step of the process according to the invention can be carried out by swirling the polycarboxylic acid obtained with the solid, preferably pulverulent neutralizing agent directly after the oxidation or post-oxidation in the fluidized bed reactor. If desired, it can be heated, preferably cooling is carried off to remove the heat of neutralization.
- Suitable mixing units are both high-speed intensive mixers, for example the CB Recycler (R) and the ploughshare FM from Lödige, and roller compactors, for example the roller compactor, so-called Shugi ( R ), sold by Alexanderwerke ( R ).
- Mixer company Hosokawa-Micron ( R )
- gentle mixers such as the mixer sold by Fima Forberg ( R ) and the Vrieco ( R ) mixer from Hosokawa-Micron ( R ).
- the neutralization step which is essential to the invention, is in fact an at least partial conversion of carboxylic acid groups into carboxylic acid salts and not a simple mixing process results from the fact that, when dissolved in water, a significantly lower heat build-up occurs than when the individual substances are simultaneously introduced into water .
- the polycarboxylates produced by the process according to the invention are preferably used for the production of solid detergents or cleaning agents because of their builders or co-builder properties.
- they are preferably used as co-builders in amounts of 0.5% by weight to 10% by weight, in particular 2% by weight to 7% by weight, based on the total weight of the composition, the inorganic Builder included as the main builder used.
- the zeolite NaA as described, for example, in connection with textile washing agents in German patent DE 24 12837, and / or layered silicates, as described in European patent application EP 164 514 are described as the main builder and polycarboxylic acid salts produced by the process according to the invention in proportions of 2: 1 to 5: 1.
- the composition of the detergents and / or cleaning agents can otherwise be chosen practically as desired in the context of known formulations.
- Starch was oxidized in the apparatus used in Example 1 of German patent application P 4426443.7.
- Nitrogen was passed through the reactor at a rate sufficient to fluidize the starch and the reactor was heated to 50 ° C.
- Nitrogen dioxide was passed through the fluidized bed from a temperature-controlled storage bottle. The gas quantities were set to 150 standard liters per hour using flow meters calibrated for air. After 4 hours, the supply of nitrogen dioxide was stopped and the reactor temperature was raised to 80 ° C. within 30 minutes and held at this temperature for 30 minutes.
- a polycarboxylic acid P1 was obtained as a white, free-flowing powder with an acid number of 371.
- 110.6 g of this oxidized starch were mixed with 150 g of a freeze-dried zeolite Na-A (OH number 274) in a stirred fixed bed with transfer for 1 hour leave nitrogen at 80 ° C.
- a powder was obtained which, when stirred into water, led to a temperature tint of + 6 ° C.
- the separate introduction of PI and the zeolite into water led to a temperature increase of 14 ° C.
- Example 3 Analogously to Example 1, 62 g of a polycarboxylic acid P2 (acid number 380) were prepared by oxidation in a fluidized bed reactor. This was left in the fluidized bed reactor, 50 g of basic sodium silicate (Portil ( R ) A) with an OH number of 472 were added and swirled with P2 over a period of 10 minutes by passing nitrogen through. A homogeneous product was obtained which remained stable even after prolonged heating to 90 ° C.
- P2 acid number 380
- Example 2 was repeated, replacing the sodium silicate with anhydrous sodium carbonate. Here too, a homogeneous product was obtained which remained unchanged after prolonged heating to 90 ° C.
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Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8526575A JPH11501345A (ja) | 1995-03-07 | 1996-02-27 | 中和した多糖系ポリカルボキシレートの製法 |
EP96905804A EP0813547B1 (de) | 1995-03-07 | 1996-02-27 | Verfahren zur herstellung von neutralisierten polycarboxylaten auf polysaccharid-basis |
US08/913,071 US5892027A (en) | 1995-03-07 | 1996-02-27 | Process for the production of neutralized polysaccharide-based polycarboxylates |
DE59601667T DE59601667D1 (de) | 1995-03-07 | 1996-02-27 | Verfahren zur herstellung von neutralisierten polycarboxylaten auf polysaccharid-basis |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19507717A DE19507717A1 (de) | 1995-03-07 | 1995-03-07 | Verfahren zur Herstellung von neutralisierten Polycarboxylaten auf Polysaccharid-Basis |
DE19507717.2 | 1995-03-07 |
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WO1996027618A1 true WO1996027618A1 (de) | 1996-09-12 |
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PCT/EP1996/000791 WO1996027618A1 (de) | 1995-03-07 | 1996-02-27 | Verfahren zur herstellung von neutralisierten polycarboxylaten auf polysaccharid-basis |
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Country | Link |
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US (1) | US5892027A (de) |
EP (1) | EP0813547B1 (de) |
JP (1) | JPH11501345A (de) |
AT (1) | ATE178911T1 (de) |
DE (2) | DE19507717A1 (de) |
ES (1) | ES2131935T3 (de) |
WO (1) | WO1996027618A1 (de) |
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DE19936613B4 (de) | 1999-08-04 | 2010-09-02 | Henkel Ag & Co. Kgaa | Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem |
CN102276732B (zh) | 2003-11-28 | 2016-01-20 | 伊士曼化工公司 | 纤维素共聚体和氧化方法 |
US9376648B2 (en) * | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
Citations (1)
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WO1993016110A1 (de) * | 1992-02-11 | 1993-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis |
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US2472590A (en) * | 1945-03-02 | 1949-06-07 | Eastman Kodak Co | Oxidation of starch with nitrogen dioxide |
AT330930B (de) * | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen |
SE419975C (sv) * | 1973-04-13 | 1986-08-18 | Henkel Kgaa | Tvett- och/eller blekmedel innehallande ett kristallint vattenolosligt silikat forfarande for dess framstellning och dess anvendning |
DE2436843A1 (de) * | 1974-07-31 | 1976-02-12 | Akzo Gmbh | Stoffgemisch aus oxydationsprodukten von cellulose, hemicellulosen und lignin |
JPS51149388A (en) * | 1975-06-17 | 1976-12-22 | Sumitomo Chem Co Ltd | A process for preparing the carboxylated pullulan |
DE2843473A1 (de) * | 1978-10-05 | 1980-04-17 | Bayer Ag | Lactonmodifizierte esteroele |
DE3041188A1 (de) * | 1980-11-03 | 1982-06-03 | Degussa Ag, 6000 Frankfurt | Vorrichtung zur oxidativen nachbehandlung von russ |
DE3413571A1 (de) * | 1984-04-11 | 1985-10-24 | Hoechst Ag, 6230 Frankfurt | Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung |
US5069919A (en) * | 1990-08-08 | 1991-12-03 | Fmc Corporation | Process for bleaching/sanitizing food fiber |
US5180398A (en) * | 1990-12-20 | 1993-01-19 | Johnson & Johnson Medical, Inc. | Cellulose oxidation by a perfluorinated hydrocarbon solution of nitrogen dioxide |
DE4402851A1 (de) * | 1994-01-31 | 1995-08-03 | Henkel Kgaa | Wirbelschicht-Oxidationsverfahren zur Herstellung von Polycarboxylaten auf Polysaccharid-Basis |
DE4426443A1 (de) * | 1994-07-26 | 1996-02-01 | Henkel Kgaa | Verbessertes Verfahren zur Herstellung von Polycarboxylaten durch Oxidation von Polysacchariden |
-
1995
- 1995-03-07 DE DE19507717A patent/DE19507717A1/de not_active Withdrawn
-
1996
- 1996-02-27 WO PCT/EP1996/000791 patent/WO1996027618A1/de active IP Right Grant
- 1996-02-27 ES ES96905804T patent/ES2131935T3/es not_active Expired - Lifetime
- 1996-02-27 EP EP96905804A patent/EP0813547B1/de not_active Expired - Lifetime
- 1996-02-27 DE DE59601667T patent/DE59601667D1/de not_active Expired - Fee Related
- 1996-02-27 JP JP8526575A patent/JPH11501345A/ja active Pending
- 1996-02-27 US US08/913,071 patent/US5892027A/en not_active Expired - Fee Related
- 1996-02-27 AT AT96905804T patent/ATE178911T1/de not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1993016110A1 (de) * | 1992-02-11 | 1993-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis |
Also Published As
Publication number | Publication date |
---|---|
EP0813547B1 (de) | 1999-04-14 |
ES2131935T3 (es) | 1999-08-01 |
EP0813547A1 (de) | 1997-12-29 |
US5892027A (en) | 1999-04-06 |
DE19507717A1 (de) | 1996-09-12 |
ATE178911T1 (de) | 1999-04-15 |
DE59601667D1 (de) | 1999-05-20 |
JPH11501345A (ja) | 1999-02-02 |
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