CN115197369A - Preparation method of graft copolymerization cationic starch - Google Patents
Preparation method of graft copolymerization cationic starch Download PDFInfo
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- CN115197369A CN115197369A CN202211017918.8A CN202211017918A CN115197369A CN 115197369 A CN115197369 A CN 115197369A CN 202211017918 A CN202211017918 A CN 202211017918A CN 115197369 A CN115197369 A CN 115197369A
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- starch
- proper amount
- agent
- graft copolymerization
- cationic starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
Abstract
The invention provides a preparation method of graft copolymerization cationic starch, which comprises the following steps: dissolving corn starch in water, adding a proper amount of an anti-swelling agent, and uniformly stirring to obtain a starch emulsion; heating to 50-60 ℃, adding an initiator and an acrylonitrile monomer, and then adding a certain amount of liquid alkali to react for 1-2h in an alkaline environment; adding a proper amount of cross-linking agent, and continuously reacting for 2-3h at 50-60 ℃; adding a certain amount of cationic etherifying agent, and preserving the heat for 4-8h at 55-65 ℃; after the etherification reaction is finished, adding a proper amount of acid to adjust the pH value to be nearly neutral, and then cooling to 35-45 ℃; after the temperature reduction is finished, adding a proper amount of bactericide into the interior of the container; cooling to room temperature, and sieving to obtain the graft copolymerization cationic starch. The invention has high reaction conversion rate and grafting efficiency, and the obtained graft copolymerization cationic starch as a papermaking wet end additive can play roles of strengthening, retention, drainage and the like and also has good auxiliary sizing effect.
Description
Technical Field
The invention relates to the technical field of preparation of starch derivatives, in particular to a preparation method of graft copolymerization cationic starch.
Background
Starch is a natural high molecular compound of polysaccharide substances formed by polycondensation of alpha-D-glucopyranose, is a renewable substance with the most abundant natural sources, can be degraded, and cannot cause pollution to the environment. A large number of reactive hydroxyl groups exist in the molecular chain of the starch, so that a structural basis is provided for the modification of the starch. The modified starch is based on the inherent characteristics of the natural starch, and in order to improve the performance of the starch and expand the application range of the starch, the physical, chemical or enzymatic treatment is utilized to introduce new functional groups on starch molecules or change the size of the starch molecules and the properties of starch granules, thereby changing the natural characteristics of the starch and enabling the starch to be more suitable for the requirements of certain applications. Since starch in nature is divided into amylose (such as corn starch) and amylopectin (such as tapioca starch), the modified starch obtained by modification has great difference in performance. The cationic starch is prepared by introducing tertiary amino or quaternary ammonium groups into starch macromolecules to endow the starch with cationic characteristics. The positive charge of cationic starch causes it to bind to the negatively charged substrate and can adsorb and hold other negatively charged additives to the substrate. A large number of experiments prove that the application performance of the cationic starch produced by the amylopectin is better than that of the amylose in the aspects of papermaking, spinning, petrochemical industry and the like, but the cost of the amylopectin is far higher than that of the amylose, so that the cost of the amylopectin is far higher than that of the amylose. Therefore, if amylose is chemically modified into a branched structure to replace amylopectin, a great cost reduction is achieved.
From the viewpoint of production process, cationic starch is produced and can be roughly classified into four types: (1) semi-drying; (2) A wet method using water as a medium, which is a common industrial production method; (3) drying; and (4) an organic solvent method. Each of these four processes has advantages and disadvantages. The semidry method has high reaction efficiency which is more than 92 percent, can prepare cationic starch with the substitution degree of more than 0.05, has the defects of more product impurities and nonuniform reaction, and mostly only occurs on the surface of starch granules, thereby influencing the use effect. The DS which can be prepared by the dry method is more than 0.1 and more is 0.1-1.0, but the problems of reagent residue and high impurity content exist, and the requirement on equipment and process is higher. The organic solvent process is limited by cost and environmental protection, and is not generally used for producing cationic starch. The wet process with water as medium is the most common cationic starch producing process in China, and has the features of homogeneous reaction and high product quality.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of graft copolymerization cationic starch, which solves the technical problems in the prior art.
The invention is realized by adopting the following technical scheme:
a preparation method of graft copolymerization cationic starch comprises the following steps:
s1, dissolving corn starch in water, adding a proper amount of an anti-swelling agent, and uniformly stirring to obtain a starch emulsion;
s2, heating the starch emulsion to 50-60 ℃, adding an initiator and an acrylonitrile monomer, and then adding a certain amount of liquid alkali to react for 1-2 hours in an alkaline environment, wherein the liquid alkali is marked as E1;
s3, adding a proper amount of cross-linking agent into the E1, and continuously reacting for 2-3h at the temperature of 50-60 ℃ and recording as E2;
s4, adding a certain amount of cationic etherifying agent into the E2, and preserving the heat for 4-8 hours at 55-65 ℃;
s5, after the etherification reaction is finished, adding a proper amount of acid to adjust the pH value to be nearly neutral, and then cooling to 35-45 ℃;
s6, after the temperature reduction is finished, adding a proper amount of bactericide into the interior of the container;
and S7, cooling to room temperature, and sieving to obtain the graft copolymerization cationic starch.
As a preferred technical scheme, the weight portions of the components are as follows: 100 parts of corn starch, 0.05-0.25 part of anti-swelling agent, 0.8-2.5 parts of initiator, 2-5 parts of acrylonitrile, 20-25 parts of liquid caustic soda, 20-24 parts of etherifying agent and 1-3 parts of bactericide.
Preferably, the anti-swelling agent is sodium sulfate or sodium chloride.
Preferably, the initiator is cerium ammonium sulfate.
Preferably, the crosslinking agent is at least one selected from epichlorohydrin or sodium trimetaphosphate.
Preferably, the etherifying agent is 3-chloro-2-hydrocyclopropyltrimethylammonium chloride or 2,3-epoxypropyltrimethylammonium chloride.
Preferably, the acid in step S5 is selected from citric acid, hydrochloric acid, sulfuric acid or acetic acid. Adding acid to adjust pH value to 6.5-7.5.
Preferably, the bactericide is at least one selected from tributyltin chloride and benzisothiazolinone.
The inventor surprisingly finds that the corn starch and acrylonitrile monomer are subjected to graft copolymerization under the action of a ceric ammonium sulfate initiator and then subjected to etherification crosslinking reaction, and the graft copolymerization cationic starch solution produced by the method has high reaction efficiency and excellent retention effect, and can greatly reduce the production cost; meanwhile, the reaction condition is mild and easy to control, and the product quality is good. The present inventors have completed the present invention based on the above findings.
The invention utilizes the cerium ammonium sulfate initiator to carry out graft copolymerization and then carry out etherification reaction, has high reaction conversion rate and grafting efficiency, and can increase the characteristics of water solubility, yield, cationic property and the like of cationic starch. The obtained high-viscosity high-substitution-degree cationic starch has high stability, uniform dispersion in cold water and good storage stability, and the graft copolymerization cationic starch can play roles of strengthening, retention, drainage and the like and has good auxiliary sizing effect as a papermaking wet-end additive.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments described below are intended to be illustrative only and are not intended to be limiting as other obvious modifications may occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
The apparatus or raw materials in the present invention are not indicated by manufacturers, and are all conventional commercial apparatuses or raw materials.
The detection indexes related to the embodiment of the invention are detected by adopting a conventional detection method in the field if not mentioned.
Example 1
Adding corn starch and deionized water into a four-opening glass-fired reaction kettle, continuously stirring, adding a proper amount of NaCl into the kettle, stirring at the speed of 450r/min, and uniformly stirring. Heating the starch emulsion to 50 ℃, adding an initiator and an acrylonitrile monomer into the starch emulsion, and adding a certain amount of liquid alkali as a catalyst to react for 1 hour in an alkaline environment, wherein the mark is E1. An appropriate amount of cross-linking agent was added to E1 and incubated at 50 ℃ for 2h, which was designated as E2. Adding a certain amount of cationic etherifying agent into the E2, and preserving the temperature at 60 ℃ for 4-8h. After the reaction is finished, adding a proper amount of acid to adjust the pH value to 6.5, and then cooling to 40 ℃. After the temperature reduction is finished, a proper amount of bactericide is added into the mixture. Cooling to room temperature, and sieving with a 325-mesh sieve to obtain the graft copolymerization cationic starch solution.
The specific values of the components in this example are as follows:
corn starch: 100g of the total weight of the mixture;
deionized water: 500g;
NaCl：0.11g；
cerium ammonium sulfate: 1.1g;
acrylonitrile: 2.5g;
3-chloro-2-hydrocyclopropyltrimethylammonium chloride: 20g of the total weight of the mixture;
NaOH solution: 20g of the total weight of the mixture;
glacial acetic acid: 6g of a mixture;
2.2g of benzisothiazolinone.
Example 2
Adding corn starch and deionized water into a four-opening glass-fired reaction kettle, continuously stirring, adding a proper amount of NaCl into the kettle, stirring at the speed of 450r/min, and uniformly stirring. The starch emulsion is heated to 50 ℃, initiator and acrylonitrile monomer are added into the starch emulsion, and a certain amount of liquid alkali is added as catalyst to react for 1 hour in alkaline environment, which is marked as E1. An appropriate amount of cross-linking agent was added to E1 and incubated at 50 ℃ for 2h, which was designated as E2. Adding a certain amount of cationic etherifying agent into the E2, and preserving the temperature at 60 ℃ for 4-8h. After the reaction is finished, adding a proper amount of acid to adjust the pH value to 6.5, and then cooling to 40 ℃. After the temperature reduction is finished, a proper amount of bactericide is added into the mixture. Cooling to room temperature, and sieving with a 325-mesh sieve to obtain the graft copolymerization cationic starch solution.
The specific values of the components in this example are as follows:
corn starch: 120g;
deionized water: 500g;
sodium sulfate: 0.15g;
cerium ammonium sulfate: 1.3g;
acrylonitrile: 2.7g;
3-chloro-2-hydrocyclopropyltrimethylammonium chloride: 22g;
NaOH solution: 24g of the total weight of the mixture;
hydrochloric acid: 5g of the total weight of the mixture;
1.5g of benzisothiazolinone.
Example 3
Adding corn starch and deionized water into a four-opening glass-fired reaction kettle, continuously stirring, adding a proper amount of NaCl into the kettle, stirring at the speed of 450r/min, and uniformly stirring. Heating the starch emulsion to 50 ℃, adding an initiator and an acrylonitrile monomer into the starch emulsion, and adding a certain amount of liquid alkali as a catalyst to react for 1 hour in an alkaline environment, wherein the mark is E1. An appropriate amount of cross-linking agent was added to E1 and the mixture was incubated at 50 ℃ for 2h, denoted as E2. Adding a certain amount of cationic etherifying agent into the E2, and preserving the temperature at 60 ℃ for 4-8h. After the reaction is finished, adding a proper amount of acid to adjust the pH value to 6.5, and then cooling to 40 ℃. After the temperature reduction is finished, a proper amount of bactericide is added into the mixture. Cooling to room temperature, and sieving with a 325-mesh sieve to obtain the graft copolymerization cationic starch solution. The specific values of the components in this example are as follows:
corn starch: 140g of the total weight of the mixture;
deionized water: 500g;
NaCl：0.11g；
cerium ammonium sulfate: 1.5g;
acrylonitrile: 2.9g;
3-chloro-2-hydrocyclopropyltrimethylammonium chloride: 24g of a mixture;
NaOH solution: 25g of the total weight of the mixture;
sulfuric acid: 5.0g;
triethyl or tributyltin chloride: 1.1g.
The graft copolymerization cationic starch solution prepared by the invention and a reference sample (commercial cationic starch) are subjected to an equal dry retention application test, and the application test effect is shown in table 1.
TABLE 1 product application Performance index
The application experiment results show that the retention effect of the graft copolymerization cationic starch solution prepared by the invention is better than that of a comparative sample.
It will be appreciated by persons skilled in the art that the above embodiments are by way of example only and are not limiting of the invention. The objects of the invention have been fully and effectively accomplished. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles.
Claims (10)
1. A preparation method of graft copolymerization cationic starch is characterized by comprising the following steps:
s1, dissolving corn starch in water, adding a proper amount of an anti-swelling agent, and uniformly stirring to obtain a starch emulsion;
s2, heating the starch emulsion to 50-60 ℃, adding an initiator and an acrylonitrile monomer into the starch emulsion, and adding a certain amount of liquid alkali into the starch emulsion to react for 1-2 hours in an alkaline environment, wherein the mark is E1;
s3, adding a proper amount of cross-linking agent into the E1, and continuously reacting for 2-3h at the temperature of 50-60 ℃ and recording as E2;
s4, adding a certain amount of cationic etherifying agent into the E2, and preserving the heat for 4-8 hours at 55-65 ℃;
s5, after the etherification reaction is finished, adding a proper amount of acid to adjust the pH value to be nearly neutral, and then cooling to 35-45 ℃;
s6, after the temperature reduction is finished, adding a proper amount of bactericide into the interior of the container;
and S7, cooling to room temperature, and sieving to obtain the graft copolymerization cationic starch.
2. The method of claim 1, wherein the weight parts of each component are as follows: 100 parts of corn starch, 0.05-0.25 part of anti-swelling agent, 0.8-2.5 parts of initiator, 2-5 parts of acrylonitrile, 20-25 parts of liquid caustic soda, 20-24 parts of etherifying agent and 1-3 parts of bactericide.
3. The method of claim 1, wherein the anti-swelling agent is sodium sulfate or sodium chloride.
4. The method of claim 1, wherein the initiator is cerium ammonium sulfate.
5. The method of claim 1, wherein the crosslinking agent is selected from at least one of epichlorohydrin or sodium trimetaphosphate.
6. The method of claim 1, wherein the etherifying agent is 3-chloro-2-hydrocropyltrimethylammonium chloride or 2,3-epoxypropyltrimethylammonium chloride.
7. The method of claim 1, wherein the acid in step S5 is selected from citric acid, hydrochloric acid, sulfuric acid, or acetic acid.
8. The method of claim 1, wherein the antimicrobial agent is selected from at least one of tributyltin chloride, benzisothiazolinone.
9. Graft copolymerized cationic starch prepared according to the process of any one of claims 1 to 8.
10. Use of the graft copolymerized cationic starch of claim 9 in wet end additives for papermaking.
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| CN202211017918.8A CN115197369A (en) | 2022-08-24 | 2022-08-24 | Preparation method of graft copolymerization cationic starch |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040170596A1 (en) * | 2003-02-28 | 2004-09-02 | Bernd Hauschel | Cationic starch graft copolymers and novel process for the preparation of cationic starch graft copolymers |
| CN105294942A (en) * | 2015-12-04 | 2016-02-03 | 东莞建泰生物科技有限公司 | Cationic grafted starch as well as production process and application thereof |
| CN108976344A (en) * | 2018-08-13 | 2018-12-11 | 武汉轻工大学 | A kind of preparation method of starch base hygroscopicity resin |
| CN112029003A (en) * | 2020-08-24 | 2020-12-04 | 上海东升新材料有限公司 | Solution type corn cationic starch and preparation method thereof |
| WO2022005423A1 (en) * | 2020-07-01 | 2022-01-06 | Ak-Kim Kimya Sanayi Ve Ticaret Anonim Sirketi | Dry and temporary wet strength additive substance for paper products |
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- 2022-08-24 CN CN202211017918.8A patent/CN115197369A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040170596A1 (en) * | 2003-02-28 | 2004-09-02 | Bernd Hauschel | Cationic starch graft copolymers and novel process for the preparation of cationic starch graft copolymers |
| CN105294942A (en) * | 2015-12-04 | 2016-02-03 | 东莞建泰生物科技有限公司 | Cationic grafted starch as well as production process and application thereof |
| CN108976344A (en) * | 2018-08-13 | 2018-12-11 | 武汉轻工大学 | A kind of preparation method of starch base hygroscopicity resin |
| WO2022005423A1 (en) * | 2020-07-01 | 2022-01-06 | Ak-Kim Kimya Sanayi Ve Ticaret Anonim Sirketi | Dry and temporary wet strength additive substance for paper products |
| CN112029003A (en) * | 2020-08-24 | 2020-12-04 | 上海东升新材料有限公司 | Solution type corn cationic starch and preparation method thereof |
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