Classifications

• • 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
  • C08B31/08—Ethers
  • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
  • C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
• • 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
  • C08B31/003—Crosslinking of starch
  • C08B31/006—Crosslinking of derivatives of starch
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
  • D21H17/24—Polysaccharides
  • D21H17/28—Starch
  • D21H17/29—Starch cationic

Definitions

• the present invention is generally directed to cationic crosslinked non-waxy starch products and their uses.
• Embodiments of the invention encompass cationic crosslinked non-waxy starch products, a method for producing the starch products, and paper products incorporating the cationic crosslinked non-waxy starch products.
• Cationic crosslinked starches are known as having an ability to improve properties such as dry strength of paper products, and an ability to improve the papermaking process by improving retention and drainage. Cationic crosslinked starches are well known products.
• US Patent Number 5,122,231 relates to cationic crosslinked starch products, that may include non-waxy starch products.
• the emphasis in this patent is related to cationic crosslinked dent starch products.
• the patent also describes the use of the cationic crosslinked starch products in the production of paper products.
• the cationic crosslinked starch products are required to have a hot paste Brookfield viscosity of about 500 cps to about 3000 cps as measured at a 1.0 Baume slurry solids which equates to 2.0% dry solids.
• US Patent Number 5,368,690 relates to cationic crosslinked starch products that are useful in the production of paper.
• the cationic crosslinked starch products are described as having a Brabender breakdown viscosity of 2 to 85%, which relates to the extent of crosslinking level.
• Various embodiments of the present invention are directed to cationic crosslinked non-waxy starch products, paper products incorporating such starch products, and methods of using such products.
• One embodiment provides a cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps (Centipoise) as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm (revolutions per minute) and at a temperature of 97 0 C.
• Another embodiment of the invention is further directed to a method for producing such cationic crosslinked non-waxy starch products.
• Further embodiments of the invention are directed to the use of such cationic crosslinked non-waxy starch products in the preparation of paper products and to paper products so made.
• Various embodiments of the present invention are directed to cationic crosslinked non-waxy starch products, paper products incorporating such starch products, and methods of using such products.
• One embodiment provides a cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps (Centipoise) as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm (revolutions per minute) and at a temperature of 97 0 C.
• Another embodiment of the invention is further directed to a method for producing such cationic crosslinked non-waxy starch products.
• Further embodiments of the invention are directed to the use of such cationic crosslinked non-waxy starch products in the preparation of paper products and to paper products so made.
• the cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C, is described as follows.
• the non-waxy starch may be derived from any suitable source such as non- waxy corn starch, non-waxy potato starch, non-waxy sweet potato, non-waxy wheat starch, non- waxy sago starch, non-waxy sorghum starch, non-waxy tapioca starch, non-waxy rice starch, and mixtures thereof.
• Non-waxy starch is defined herein as starch containing both amylose and amylopectin.
• Non-waxy starch products in embodiments of the present invention have a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• the Brookfield viscosity ranges from about 800 cps to about 2000 cps.
• the Brookfield viscosity ranges from about 1000 cps to about 1500 cps. The test procedure for determining the Brookfield viscosity is described herein.
• any conventional method may be used such as those disclosed in US Patent Number 5,122,231 and US Patent Number 5,368,690 that relate to methods for preparing cationic crosslinked starches.
• any non-waxy starch may be cationized and crosslinked, in either order or simultaneously, and the reaction may be allowed to proceed under conditions to produce a cationic, crosslinked non-waxy starch having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• the process is carried out under conditions that will produce a cationic crosslinked non-waxy starch having a viscosity of from about 800 cps to about 2000 cps, and more preferably, from about 1000 cps to about 1500 cps.
• the non-waxy starch utilized in the process may be any of the non-waxy starches identified above. In one useful embodiment, the non-waxy starch is non-waxy corn starch.
• cationizing agent may be utilized in the process, it is preferred that the cationizing reaction be achieved utilizing a component selected from an amino ion, imino ion, sulfonium ion, phosphonium ion, ammonium ion and mixtures thereof, preferably, a quaternary ammonium ion.
• crosslinking agents are suitable for use in the present process, embodiments of the invention utilize a component selected from a multi-functional etherifying agent, a multi-functional esterifying agent and mixtures thereof.
• Suitable crosslinking agents for select embodiments are epichlorohydrin, a dicarboxylic anhydride, phosphorous oxychloride, an alkali earth metal salt of trimetaphosphate, a linear mixed anhydride, a polyamine polyepoxide resin and mixtures thereof.
• One preferred embodiment employs an alkali earth metal salt of trimetaphosphate as the crosslinking agent.
• preparing the cationic crosslinked non-waxy starch products includes generally monitoring the reaction for completion by measuring the viscosity to ensure that the viscosity value ranges from about 700 cps to about 2500 cps as measured by the test procedure herein. When the viscosity is determined to fall within the desired range, the reaction may be terminated.
• a non-waxy starch is cationized by reacting the non-waxy starch with any cationizing agent.
• exemplary of the cationizing agents are agents having amino ions, imino ions, sulfonium ions, phosphonium ions, or ammonium ions and mixtures thereof.
• the cationizing reaction may be carried out in any conventional manner such as reacting the non-waxy starch in an aqueous slurry form with the cationizing agent, usually in the presence of an activating agent such as sodium hydroxide.
• Another process that may be used is a semi-dry process where the non-waxy starch is reacted with the cationizing reagent in the presence of an activating agent such as sodium hydroxide, in a limited amount of water.
• the cationizing agent has an ammonium ion, and preferably, the ammonium ion is a quaternary ammonium ion.
• the ammonium ion is a quaternary ammonium ion.
• One particularly useful embodiment employs (3- chloro-2-hydroxypropyl)trimethylammonium chloride as a cationizing agent.
• the cationic crosslinked non-waxy starch products are crosslinked by reacting the non-waxy starch with any crosslinking agent.
• the reaction is carried out using any known manner for crosslinking a product.
• Suitable crosslinking agents for some embodiments include, but are not limited to, a multi-functional etherifying agent, a multi-functional esterifying agent, mixtures thereof, and the like.
• crosslinking agents include, but are not limited to, epichlorohydrin, a dicarboxylic anhydride, phosphorous oxychloride, an alkali earth metal salt of trimetaphosphate, a linear mixed anhydride, a polyamine polyepoxide resin, mixtures thereof, and the like.
• the crosslinking reaction may be carried out in any conventional manner such as reacting the non-waxy starch in an aqueous slurry form with the crosslinking agent, usually in the presence of an activating agent such as sodium hydroxide.
• Another crosslinking process that may be used is a semi-dry process where the non-waxy starch is reacted with the crosslinking agent in the presence of an activating agent such as sodium hydroxide, in a limited amount of water.
• the non-waxy starch may be cationized and crosslinked in any order, in producing the cationic crosslinked non-waxy starch.
• the starch may be cationized then crosslinked, or the starch may be crosslinked then cationized.
• the cationizing agent and the crosslinking agent may be utilized simultaneously.
• Some embodiments of the invention employ cationic crosslinked non-waxy starch products in the production of paper.
• the cationic crosslinked non-waxy starch products may be incorporated in the production of paper using any conventional manner.
• the cationic crosslinked non-waxy starch products may be slurried in water and the resultant slurry heated at a temperature sufficient to achieve gelatinization of the starch slurry to produce a gelatinized starch paste.
• the heating to achieve gelatinization is carried out at a temperature above about 90 °C.
• the gelatinized starch paste may then be applied to a cellulosic suspension, particularly a paper furnish, in any known manner.
• the gelatinized starch paste may be applied to the wet- end of a paper machine in a paper fiber thick stock, or a paper fiber thin stock, or a split addition to both the thick stock and thin stock.
• any amount of starch may be incorporated as desired.
• the amount of cationic crosslinked non-waxy starch to be incorporated ranges from about 0.1% to about 5% by weight based on the paper fiber.
• the cationic crosslinked non-waxy starch product is present in an amount ranging from about 0.5% to about 2% by weight based on the weight of the fiber.
• additives may be utilized in producing the paper products.
• Cationic crosslinked non-waxy starch products in accordance with aspects of the present invention are expected to have utility in fields other than papermaking. Such applications would include, for example, food container manufacture, production of paints, flocculation of aqueous suspensions as in water treatment and ore purification, and the like. [0019]
• the following examples are presented to illustrate aspects of the present invention and to assist one of ordinary skill in making and using the same. The examples are not intended in any way to otherwise limit the scope of the invention.
• Brookfield viscosity of a cationic crosslinked non-waxy starch was determined in accordance with the Standard Analytical Methods of the Corn Refiners Association, Inc. Test Procedure CRA Method B-54 with the conditions specified herein.
• the instrument utilized in determining viscosity was a Brookfield DV-II+ Viscometer. The test procedure was conducted by cooking a sample, at a hot water bath temperature setting of 97 0 C, for 10 minutes using spindle number 21 at 20 revolutions per minute.
• Cationic crosslinked non-waxy corn starch having a Brookfield viscosity within the range of 700 cps to 2500 cps is prepared by charging a reactor with non-waxy corn starch slurry, sodium hydroxide, and (3-chloro-2-hydroxypropyl) trimethylammonium. The slurry is then heated and allowed to react for a required period of time to achieve a desired nitrogen substitution. After the nitrogen substitution is achieved, a sample of the slurry is measured to ensure that the pH of the reaction slurry was at 11.2. If necessary, the pH is adjusted to 11.2. Sodium trimetaphosphate is added in one portion to the slurry and the slurry is allowed to react for a designated period of time.
• the slurry is brought to a pH of about 7 by the addition of an acid solution.
• the slurry is then washed, de-watered, and dried to a desired moisture level.
• the viscosity of the resulting cationic crosslinked non-waxy starch is determined by the Brookfield viscosity procedure herein.
• An alternative embodiment of producing the cationic crosslinked non-waxy starch of the present invention is as follows. Semi-dry non-waxy corn starch, having a moisture level of 10-30% is mixed with 2,3-epoxypropyl-N,N,N,-trimethylammonium chloride, and l,3-dichloro-2- propanol in the presence of sodium hydroxide as an activating agent.
• cationic crosslinked non-waxy corn starch having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Example 1 The process according to Example 1 is followed with the exception that (3-chloro- 2-hydroxypropyl)trimethylammonium chloride is replaced by (3-chloro-2- hydroxypropyl)dimethyldodecylammonium chloride. It is expected that there will be obtained cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Example 1 The process according to Example 1 is followed with the exception that (3-chloro- 2-hydroxypropyl)trimethylammonium chloride is replaced by (3-chloro-2- hydroxypropyl)dimethyloctadecylammonium chloride. It is expected that there will be obtained cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Example 1 The process according to Example 1 is followed with the exception that the sodium trimetaphosphate is replaced by 1,2,4,5-benzenetetracarboxylic dianhydride and is reacted at a pH range of 8-10. It is expected that there will be obtained cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Example 1 The process according to Example 1 is followed with the exception that the non- waxy corn starch is replaced by non-waxy rice starch. It is expected that there will be obtained cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Example 1 The process according to Example 1 is followed with the exception that the non- waxy corn starch is replaced by non-waxy tapioca starch. It is expected that there will be obtained cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Example 8 [0040] The process according to Example 1 is followed with the exception that the non- waxy corn starch is replaced by non-waxy potato starch. It is expected that there will be obtained cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• Example 2 The process according to Example 1 is followed with the exception that the non- waxy corn starch is replaced by non-waxy sorghum starch. It is expected that there will be obtained cationic crosslinked non-waxy starch product having a Brookfield viscosity ranging from about 700 cps to about 2500 cps as measured in accordance with CRA Method B-54 at 0.5% solids using spindle number 21 at 20 rpm and at a temperature of 97 0 C.
• a cationic crosslinked non-waxy corn starch product prepared in Example 1 in the preparation of a paper product.
• the starch product is utilized in the form of a gelatinized paste.
• the paper is prepared using a standard Fourdrinier paper machine.
• the hardwood/softwood bleached fiber is added to a coated broke furnish at the blend chest along with ground calcium carbonate and thick stock alum in conventional amounts.
• the furnish mixture is further diluted with water, followed by the addition of a starch paste.
• silica and trim alum in conventional amounts are added and the furnish is pumped to the headbox for distribution onto the paper machine wire.
• the paper web is then dried and wound on a roll.
• Example 11 [0047] In this example the procedure of Example 10 is followed with the exception that the cationic crosslinked non-waxy corn starch of Example 1 is replaced by the cationic crosslinked non- waxy corn starch of Example 2. It is expected that there will be obtained a suitable paper product.
• Example 10 the procedure of Example 10 is followed except that the cationic crosslinked non-waxy corn starch of Example 1 is replaced by, respectively, the cationic crosslinked non-waxy corn starch products of Examples 3, 4, and 5. It is expected that there will be obtained suitable paper products. In these instances it is further expected that the paper product produced using the starch products of Examples 3, 4, and 5 will be characterized by increased internal sizing.
• Example 10 the procedure of Example 10 is followed with the exception that the cationic crosslinked non-waxy corn starch of Example 1 is replaced by the cationic crosslinked non- waxy rice starch product of Example 6. It is expected that there will be obtained a suitable paper product.
• Example 10 In this example the procedure of Example 10 is followed with the exception that the cationic crosslinked non-waxy corn starch of Example 1 is replaced by the cationic crosslinked non- waxy tapioca starch product of Example 7. It is expected that there will be obtained a suitable paper product.
• Example 10 In this example the procedure of Example 10 is followed with the exception that the cationic crosslinked non-waxy corn starch of Example 1 is replaced by the cationic crosslinked non- waxy potato starch product of Example 8. It is expected that there will be obtained a suitable paper product.
• Example 10 In this example the procedure of Example 10 is followed with the exception that the cationic crosslinked non-waxy corn starch of Example 1 is replaced by the cationic crosslinked non- waxy sorghum starch product of Example 9. It is expected that there will be obtained a suitable paper product.

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• 2005
  • 2005-05-04 BR BRPI0512231-7A patent/BRPI0512231A/pt not_active Application Discontinuation
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  • 2005-05-04 CN CNA2005800196707A patent/CN1968969A/zh active Pending
  • 2005-05-04 RU RU2007101371/04A patent/RU2007101371A/ru unknown
  • 2005-05-04 EP EP05740295A patent/EP1773889A1/en not_active Withdrawn
  • 2005-05-04 CA CA002570850A patent/CA2570850A1/en not_active Abandoned
  • 2005-05-04 WO PCT/US2005/015567 patent/WO2006007045A1/en active Application Filing
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