WO1992015535A1 - Acide polyaspartique et ses sels pour la dispersion de solides en suspension - Google Patents
Acide polyaspartique et ses sels pour la dispersion de solides en suspension Download PDFInfo
- Publication number
- WO1992015535A1 WO1992015535A1 PCT/US1992/001704 US9201704W WO9215535A1 WO 1992015535 A1 WO1992015535 A1 WO 1992015535A1 US 9201704 W US9201704 W US 9201704W WO 9215535 A1 WO9215535 A1 WO 9215535A1
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- WIPO (PCT)
- Prior art keywords
- finely divided
- divided solid
- aqueous suspension
- solid particles
- temperature
- Prior art date
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- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 34
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 31
- 150000003839 salts Chemical class 0.000 title claims abstract description 11
- 239000007787 solid Substances 0.000 title claims description 26
- 239000002245 particle Substances 0.000 claims description 29
- 239000007900 aqueous suspension Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000010954 inorganic particle Substances 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011146 organic particle Substances 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229920003176 water-insoluble polymer Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 description 55
- 239000011541 reaction mixture Substances 0.000 description 26
- 239000003921 oil Substances 0.000 description 23
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 20
- 229960005261 aspartic acid Drugs 0.000 description 20
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 19
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000004584 polyacrylic acid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- -1 BaSO„ Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000608 Polyaspartic Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/28—Aminocarboxylic acids
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- 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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
Definitions
- Examples of the different types of scale and particulates dispersed would include CaC0 3 , CaS0 4 , BaSO Region, Fe 2 0 3 , clays such as Kaolin, Ti0 2 , Zn(0H) 2 , Ca 3 (P0) 4 , Mg(0H) 2 , Mn 2 0 3 and many others.
- dispersants used today are of a synthetic variety, usually a water soluble polymer made from acrylic acid, acrylamide, their derivates, maleic acid, vinyl esters, and the like. These polymers are non-biodegradable and potentially toxic to the environment.
- Starch and lignin based dispersants although biodegradable, tend to be poorer performers compared to their polyacrylate counterparts.
- Water soluble salts of polyaspartic acid are excellent agents for suspending in water a variety of inorganic and organic particles. Due to the biodegradability of polyaspartic acid it is acceptable for use in a variety of industrial products and processes.
- FIGURE 1 depicts a temperature versus time reaction curve.
- Series 1 is the oil temperature.
- Series 2 is the reaction mixture temperature.
- FIGURE 2 depicts a temperature versus time reaction curve.
- Series 1 is the oil temperature.
- Series 2 is the reaction mixture temperature.
- FIGURE 3 depicts a temperature versus time reaction curve.
- Series 1 is the oil temperature.
- Series 2 is the reaction temperature.
- FIGURE 4 depicts a temperature versus time reaction curve.
- Series 1 is the oil temperature.
- Series 2 is the reaction temperature.
- FIGURE 5 depicts a temperature versus time reaction curve.
- Series 1 is the oil temperature.
- Series 2 is the reaction mixture temperature.
- the starting polysuccinimides from which the polyaspartic acids are synthesized are produced by the thermal condensation of powdered L-aspartic acid to produce polysuccinimide in high yields.
- yield means theoretical yield based on the starting molecular weight of the aspartic acid. These yields optimally occur above the initiation temperature of about 370 °F and preferably occurs above 420 °F, and most preferably occurs above 440 °F.
- a reactant temperature less than 370 °F may produce polysuccinimide over a period of many hours.
- Theoretical yields will be low; the conversion of the L-aspartic acid to polysuccinimide will be less than 70% and will require a period of many days.
- the thermal condensation of L-aspartic acid to polysuccinimide using the above reaction conditions produces a characteristically shaped "temperature vs. time" reaction curve.
- the curve is characterized by an initial, rapid rise in reactant temperature, followed by an endotherm signally the beginning of the reaction. Immediately following the onset of the endotherm there is evaporative cooling, followed first by a temperature rise, and then by a second endotherm, which is followed by an evaporative cooling plateau. The temperature then rises to a plateau. That plateau is at a constant temperature. The reaction has gone to at least 95% conversion at the temperature midway between the final plateau and the time the temperature begins to rise to that plateau.
- the color of each product sample was noted.
- the color of L-aspartic acid is white.
- Polysuccinimides vary in color according to the temperature of the sample taken during the course of the reaction. From low temperature to high, the colors vary as follows: light pink, to pink, to tannish pink, to tan, to light yellow, to yellow. These colors generally correspond to the percent conversion of the L- aspartic acid, in the same order with light pink indicating the lowest percent conversion and yellow indicating the highest percent conversion. The pink colors had less than 70 % conversion.
- the literature has never reported any other color but pink.
- the polysuccinimides used in the practice of this invention should be free of pure pink color.
- the polysuccinimides used to prepare the polyaspartic acid dispersants of this invention have a water content less than 1%, and they usually are substantially water-free.
- the conversion of L-aspartic acid to polysuccinimide was determined as follows: A specific amount of the reaction mixture or product was dissolved in an aliquot of dimethylformamide (DMF). The dissolution was allowed to proceed for 4 to 5 hours until all of the polysuccinimide dissolved in the DMF leaving unreacted L-aspartic acid which was filtered out.
- DMF dimethylformamide
- the amount of unreacted L-aspartic acid was determined by using the following formula:
- the percent conversion of the L-aspartic acid to the polysuccinimide in the reaction can be increased in reduced time periods by increasing the temperatures used.
- thermal fluid is used to heat the L-aspartic acid and as its temperature is brought to a maintenance temperature of at least 550 ⁇ F in a reasonable time period, at least 90% conversion can be effected within 4 hours.
- thermal fluid used to heat the L-aspartic acid is brought to a maintenance temperature of at least 550 °F within a reasonable time period, at least 90% conversion can be effected within 2 hours.
- Continuous and batch processes can be used. Some process examples include fluidized bed, stirred reactor, and indirectly heated rotary driers.
- temperatures between 420-520 °F produces polysuccinimide at yields greater than 80%.
- temperatures between 420-450 °F 90% conversions will be obtained.
- 500 °F will produce a 90% conversion in 4 hours and 510 °F will produce a 90% conversion in 1 1/2-2 hours.
- the reaction began when the first endotherm was reached.
- the first endotherm of the reaction mixture peaked at 395 °F at an oil temperature of 439 °F.
- the color of the reaction mixture is provided. Color was observed to vary with product temperature.
- the reaction began when the first endotherm was reached.
- the first endotherm of the reaction mixture peaked at 405 °F at an oil temperature of 465 °F.
- Table 2 below provides data developed during this experiment. Samples were taken at the times indicated and analyzed for percent conversion to polysuccinimide.
- the color of the reaction mixture is provided. Color was observed to vary with product temperature.
- the reaction began when the first endotherm was reached.
- the first endotherm of the reaction mixture peaked at 410 °F at an oil temperature of 470 °F.
- the color of the reaction mixture is provided. Color was observed to vary with product temperature.
- a DVT-130 drier, mixer manufactured by the Littleford Brothers, Inc., of Florence, Kentucky was used.
- the jacketed drier utilizes a thermal fluid (hereinafter called "oil"), a plough blade impeller, a stack open to the atmosphere; and has a heat transfer area of 10 ft 2 .
- the reactor's oil reservoir was preheated to 550 °F.
- the reactor was charged with 110.4 lb of powdered, L-aspartic acid. Hot oil began to flow through the jacket, and the impeller speed was set at 155 rpm. Both the product and oil temperatures rose steadily. At a product temperature of 390 °F, there was a sudden, endothermic reaction which caused the product temperature to drop (see Fig. 4). Water loss was evidenced by the evolution of steam. A sample taken revealed that the powder had changed from white to pink. Three percent of the material was converted to polysuccinimide.
- Table 4 below provides data developed during this experiment. Samples were taken at the times indicated and analyzed for percent conversion to polysuccinimide.
- Polysuccinimides may be produced using the steps of a) . heating powdered L-aspartic acid to at least 370 ⁇ F to initiate the condensation reaction, then b). raising the reaction mixture temperature to at least 420 °F, and c) . maintaining at least the 420 °F temperature until at least 80% conversion has occurred.
- reaction mixture temperature is raised to at least 430 °F for a sufficient period of time a 90 % conversion can be achieved.
- reaction mixture temperature is raised to at least 440 °F for a sufficient period of time a 95% conversion can be achieved.
- Polyaspartic acid is produced from polysuccinimide using the following hydrolysis procedure: A slurry is made from a measured amount of polysuccinimide and distilled water. Sodium hydroxide is added dropwise to hydrolyze polysuccinimide to polyaspartic acid. The completion of the hydrolysis is attained at pH 9.5.
- Bases other than sodium hydroxide can be used. Suitable bases include ammonium hydroxide, potassium hydroxide, and other alkaline and alkaline earth hydroxides.
- base should be added to the slurry until the pH has been raised to 9.5, and a clear solution has been formed.
- the pH may be adjusted to higher levels. Between pHs ranging between 11 and 12, the polaspartic acid solutions have a bright yellow color. These higher pH solutions are useful when compatibility with higher pH slurries is required.
- Polyaspartic acids are made up of alpha and beta peptide bonds.
- the polyaspartic acids used as dispersants to practice this invention contain between 50% to about 75% of beta peptide groups.
- the preferred dispersants usually contain 60% to 75% of beta peptide bonds.
- polyaspartic acid used herein and in the claims means the salts of polyaspartic acid.
- Counterions for polyaspartate include, but are not limited to, the alkaline and alkaline earth cations, some examples of which are Na + , K + , Mg + , and Li + , Ca ++ , Zn ++ , Ba ++ , Co ++ , Fe ++ , Fe +++ , and NH4 + .
- the free acid is very water soluble therefore making it of extended applicability as a dispersant.
- MOLECULAR WEIGHT DETERMINATION The polyaspartic acid dispersant of this invention has a weight average molecular weight of 1000 to 5000.
- the suspended solids capable of being effectively suspended b y the polyaspartic acid salts include a wide variety of both inorganic and organic particles. 1. THE INORGANIC PARTICLES
- alumino-silicates which encompass a wide number of clays.
- the alumino-silicates also include a large number of inorganic ion exchange materials illustrated by the base exchange clays and the synthetic zeolites illustrated by the molecular seives. It is obvious to those skilled in the art that certain of the alumino-silicates described above contain elements other than aluminum, silicon, and oxygen. When such additional elements are present for instance, magnesium, the solids are considered to be alumino-silicates.
- a particlularly broad class of inorganic particles capable of being suspended by the polyaspartic acid salts may be generically described as pigments.
- Illustrative of such materials are the finely divided particles calcium carbonate, titania, and silica. These materials find use in the form of aqueous suspension in the manufacture of paints, paper, ceramic slurries and many other well known commercial products.
- the invention is particularly useful in its ability to produce stabilized iron oxide suspensions.
- These particles include a wide variety of organic materials illustrated by such materials as dirt, which includes silt.
- Other such organic materials are carbon particles and a variety of finely divided water insoluble polymers which are often found in coating compositions in the form of latexes.
- Illustrative of such latexes would be polystyrene, polyvinylchloride, polyacrylonitrile, synthetic rubbers, e.g., polybutadienes and the like.
- a particlularly useful application for the suspending agents of the invention is their use in the suspension polymerization of a variety of water insoluble polymers.
- the suspended solids that may be suspended using the polyaspartic acid salts described herein will vary between as little as 0.01 micron upto particles as large as about 1 centimeter. Typical particle sizes of this suspended solids will be in the range of 50-500 microns. In describing particle sizes it is understood that they are described with respect to the average particle size of the particular particles present in a given suspension.
- DOSAGE The amount of water soluble salt of the poly aspartic acid used to suspend a variety of solids in water may range between 0.5-200 ppm. A typical dosage to suspend clays, iron oxides, dirt and the like is within the range of 1-50 ppm. The optimum dosage will depend upon the particular polyaspartic acid salt used, The ph of aqueous suspension and the nature of the particles with respect to their composition and size.
- Kaolin Dispersion 1 g/L of kaolin was mixed with CaCl-,.2H 2 0. The pH of the slurry was adjusted and poured into 100 ml graduated cylinders. Known concentrations of dispersants were then added to the cylinders and thoroughly mixed.
- the samples were also scanned with UV/VIS from 900 nm to 200 nm and the absorbance recorded at 450 nm.
- Kaolin Dispersion with Fe 3+ This assay follows the same procedures as the kaolin dispersion test except 2.5 ppm ferric chloride are added to each graduated cylinder. The following data compares polyaspartic acid with polyacrylic acid. The results are as follows :
- Control Polyaspartic Acid Polyacrylic Acid ppm 0 10 50 100 10 50 100 NTU (2 hours) 36 150 120 150 150 140 140 ABS (2 hours) O.ll 0.89 0.38 0.92 0.66 0.48 0.47
- Ferric Oxide Dispersion 700 ppm Fe as Fe 2 0 3 were mixed with 200 ppm Ca 2 * as CaC0 3 .
- the pH of the slurry was adjusted to a fixed value.
- the solution was thoroughly mixed.
- the slurry was transferred to 100 ml graduated cylinders and known concentrations of dispersants were added.
- Titanium Dioxide Dispersion lg/L of titanium dioxide was mixed with 200 ppm Ca 2+ as CaC0 3 and adjusted to a fixed pH. The solution was thoroughly stirred and poured into 100 ml graduated cylinders. Known concentrations of inhibitor were added.
- Control Polyaspartic Acid Polyacrylic Acid ppm 0. 1 10 100 1 10 100 NTU(2 hours) 282 320 412 459 331 480 594 NTU(24 hours) 21 22 36 49 23 41 44
- Zinc Hydroxide Dispersion 250 ppm of Ca 2+ as CaC0 3 and 125 ppm Mg 2+ as CaC0 3 were made into a solution. An inhibitor was added at this time prior to the addition of O.Olg/L of zinc chloride. Equal amount of sodium hydroxide was added for each test. White precipitate of zinc hydroxide was evident. The ability of the dispersant was tested using nephelometric turbidity. The higher the NTU, the better the dispersant. Here were the results of each testing.
- the polyaspartic acid used in all the above examples corresponds to the polyaspartic acid produced in the pilot plant test run.
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Abstract
L'invention se rapporte à des sels d'acide polyaspartique d'un poids moléculaire compris entre 1 000 et 5 000, qui constituent d'excellents agents dispersants.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US65510191A | 1991-03-06 | 1991-03-06 | |
US655,101 | 1991-03-06 |
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WO1992015535A1 true WO1992015535A1 (fr) | 1992-09-17 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1992/001704 WO1992015535A1 (fr) | 1991-03-06 | 1992-03-05 | Acide polyaspartique et ses sels pour la dispersion de solides en suspension |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5538671A (en) * | 1992-10-27 | 1996-07-23 | The Procter & Gamble Company | Detergent compositions with builder system comprising aluminosilicates and polyaspartate |
EP0736596A1 (fr) * | 1995-04-03 | 1996-10-09 | The Procter & Gamble Company | Compositions pour trempage |
FR2759611A1 (fr) * | 1997-02-14 | 1998-08-21 | Coatex Sa | Nouvelle utilisation de sels d'acides polyaspartiques comme agent d'aide au broyage |
US5804639A (en) * | 1995-10-31 | 1998-09-08 | Bayer Ag | Pigment preparations having a high solids content |
WO2000000579A1 (fr) * | 1998-06-26 | 2000-01-06 | Aware Chemicals L.L.C. | Procede pour nettoyer des pieces d'une installation de laquage, servant a alimenter en peinture, notamment des conduites de peinture |
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US3846380A (en) * | 1972-10-31 | 1974-11-05 | M Teranishi | Polyamino acid derivatives and compositions containing same |
US4534881A (en) * | 1983-12-19 | 1985-08-13 | University Of South Alabama | Inhibition of inorganic or biological CaCO3 deposition by poly amino acid derivatives |
US4640943A (en) * | 1983-09-22 | 1987-02-03 | Ajinomoto Co., Inc. | Surface modifier for inorganic substances |
US4732693A (en) * | 1985-07-29 | 1988-03-22 | Lever Brothers Company | Soap-nonionic detergent compositions containing a cellulose ether anti-redeposition agent |
US4839461A (en) * | 1986-08-07 | 1989-06-13 | Bayer Aktiengesellschaft | Polyaspartic acid from maleic acid and ammonia |
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1992
- 1992-03-05 WO PCT/US1992/001704 patent/WO1992015535A1/fr active Application Filing
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US3846380A (en) * | 1972-10-31 | 1974-11-05 | M Teranishi | Polyamino acid derivatives and compositions containing same |
US4640943A (en) * | 1983-09-22 | 1987-02-03 | Ajinomoto Co., Inc. | Surface modifier for inorganic substances |
US4534881A (en) * | 1983-12-19 | 1985-08-13 | University Of South Alabama | Inhibition of inorganic or biological CaCO3 deposition by poly amino acid derivatives |
US4732693A (en) * | 1985-07-29 | 1988-03-22 | Lever Brothers Company | Soap-nonionic detergent compositions containing a cellulose ether anti-redeposition agent |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5538671A (en) * | 1992-10-27 | 1996-07-23 | The Procter & Gamble Company | Detergent compositions with builder system comprising aluminosilicates and polyaspartate |
EP0736596A1 (fr) * | 1995-04-03 | 1996-10-09 | The Procter & Gamble Company | Compositions pour trempage |
US5804639A (en) * | 1995-10-31 | 1998-09-08 | Bayer Ag | Pigment preparations having a high solids content |
DE19540557B4 (de) * | 1995-10-31 | 2007-03-29 | Lanxess Deutschland Gmbh | Pigmentpräparationen mit hohem Feststoffgehalt |
FR2759611A1 (fr) * | 1997-02-14 | 1998-08-21 | Coatex Sa | Nouvelle utilisation de sels d'acides polyaspartiques comme agent d'aide au broyage |
EP0860477A1 (fr) * | 1997-02-14 | 1998-08-26 | Coatex S.A. | Utilisation de sels d'acides polyaspartiques comme agent d'aide au broyage |
US5998526A (en) * | 1997-02-14 | 1999-12-07 | Coatex S.A. | Use of salts of polyaspartic acids as milling agents |
WO2000000579A1 (fr) * | 1998-06-26 | 2000-01-06 | Aware Chemicals L.L.C. | Procede pour nettoyer des pieces d'une installation de laquage, servant a alimenter en peinture, notamment des conduites de peinture |
US6475295B1 (en) | 1998-06-26 | 2002-11-05 | Aware Chemicals L.L.C. | Method for cleaning the paint feeding parts of a painting installation, especially the paint lines |
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