CN115141576B - Preparation method and application of starch-based material for adhesive - Google Patents
Preparation method and application of starch-based material for adhesive Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
- C09J103/10—Oxidised starch
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- 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
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
Abstract
The invention relates to the field of adhesive materials, and discloses a preparation method and application of a starch-based material for an adhesive.
Description
Technical Field
The invention relates to the field of adhesive materials, in particular to a preparation method and application of a starch-based material for an adhesive.
Background
The solidifying adhesive used in the market at present mainly comprises two types, namely an adhesive product obtained by formalizing polyvinyl alcohol (PVA) as a raw material and an adhesive obtained by polyvinyl pyrrolidone (PVP) as a raw material. Because the adhesive prepared by using polyvinyl alcohol (PVA) has the inherent defects of comprehensive properties such as adhesion and the like, the adhesive cannot be used as an independent main material, a certain amount of formaldehyde is required to be added for modification to obtain the polyvinyl formal (PVFM) adhesive, but the adhesive has the problems of high free formaldehyde content, heavy smell, poor adhesion performance, intolerance of storage, poor hardness and smearing performance, and has extremely high harm to human bodies in the use process, particularly after the adhesive which is cheap and harmful to teenagers and children is used, the adhesive can bring physical injury to different degrees, and the PVFM adhesive is limited in export due to the problems of excessive fluorescent substance addition, color improvement and the like. The coagulating adhesive produced by using PVP as a main material has excellent comprehensive properties such as cohesiveness, environmental protection and the like, is used by most enterprises and is used for export to various places in the world, but because the raw materials are mostly polymerized by using calcium carbide and petroleum-based ethylene polymerization monomers at present, the raw materials mainly depend on petrochemical resources, have extremely high price and are not renewable, and are only used for production and export of high-end products by most adhesive production enterprises, the application and popularization are limited by different degrees.
Starch is a carbohydrate formed by photosynthesis of plants, is widely available and low in cost, returns to the nature in the form of carbon dioxide and water after degradation, is considered as a natural renewable material completely free of pollution, and is widely researched and developed in various fields. However, the starch or a single modified product has the defects of high viscosity, poor stability and shearing resistance, insufficient heat and alkali resistance, brittle and hard film formation and the like, so that the starch or the single modified product is difficult to be independently used as a polymer material to be applied to the special adhesive industry. The chemical modification of starch, including acidolysis, esterification, etherification, oxidation, crosslinking, etc., has been initiated as early as the 40 th century of 20. Starch from different sources can be obtained by adopting different denaturation methods and different denaturation degrees, starch materials with different properties and new physical and chemical characteristics can be obtained, and the performance of the modified starch is greatly improved, so that the modified starch can be widely used in the traditional fields of papermaking, textiles, foods, medicines, feeds, water-absorbing materials, water treatment, foaming agent materials and the like, and can also be used for preparing biodegradable plastics, tissue engineering brackets, carriers for drug release, carriers for bioactive substances and the like, and the modified starch can be widely used in various industries as a renewable pollution-free natural renewable resource material.
Patent CN102925075A discloses a biological starch-based solid adhesive and a preparation method thereof, and specifically, waxy corn starch and water are mixed, gelatinized at a certain temperature and time, cooled, added with amylase for enzymolysis reaction, then subjected to vacuum dehydration and cyclodextrin enzyme treatment, subjected to complexation and oxidation reaction for a certain time, deactivated, added with fatty acid, and simultaneously adjusted to pH value of 8.5-10 by NaOH solution, and added with preservative to obtain the biological starch-based solid adhesive. Patent CN114213997a discloses an environment-friendly degradable plant solid glue stick, in particular to a novel product which is prepared by using fatty acid salt as an excipient, glycerol as a humectant, hydroxypropyl starch ether and oligosaccharide as adhesives, and has the advantages of simplicity, convenience, strong initial adhesion, high adhesive strength, good adhesive force, high drying speed, long adhesive time, safety, environment friendliness and no harm to human body. However, the patent only mentions that a hydroxypropyl starch ether and an oligosaccharide are needed for the addition of the adhesive, and does not specify the index of the hydroxypropyl starch ether used and the preparation process thereof.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a starch-based material for an adhesive, and the invention provides a novel starch modification route (starch is subjected to wet heat treatment, etherification, acidolysis and oxidization, and a composite property improver is added) for modifying and recombining molecular groups of starch, and the obtained starch-based material has the characteristics of excellent smearing performance, good cohesiveness, high hardness, high temperature resistance, alkali resistance and the like.
The specific technical scheme of the invention is as follows: the preparation method of the starch-based material for the adhesive comprises the following steps:
(1) Mixing starch and water, stirring to obtain slurry, adding alkaline regulator to regulate pH to 6.8-7.2, adding magnesium salt, heating, maintaining temperature, and stirring for reaction.
In the step (1), the starch is subjected to wet heat treatment under a specific pH value range, so that when the starch slurry is subjected to high-temperature wet heat treatment under a neutral condition, the starch molecules can be continuously strengthened and stabilized to perform wet heat reaction within a proper acid-base range, and if the pH value is too low and too high, the risk of chain breakage of the starch molecules is greatly brought, and the polymerization degree of the starch molecules cannot be controlled due to long-time treatment. After the treatment according to step (1) of the present invention, the gelatinization temperature of the starch may be increased from about 65 ℃ to about 75 ℃ and the peak temperature may be increased from 75.0 ℃ to 90-92 ℃. Through data analysis, the retrogradation characteristic of the starch is obviously improved through the process treatment of the section. Meanwhile, the addition of a proper amount of magnesium salt crystals provides a guarantee for keeping the birefringence characteristics of starch granule molecular crystals in a long-time high-temperature system environment, after the binding force of starch molecular hydrogen bonds is enhanced, the anti-swelling characteristic is improved, and necessary conditions are created for the modification treatment of reagents with higher addition amount, such as etherification, oxidization and the like, of the later-stage starch under the deep wet condition, so that the starch modified material with the optimal molecular state and alkali resistance can be obtained within a certain limit index range, otherwise, the recovery rate and the modification degree of the later-stage starch material are greatly influenced, and the application effect of the starch modified material in the solidification type adhesive is greatly reduced.
(2) Adding an alkaline regulator to regulate the pH value to 10.0-12.0, adding an antigelling agent, a surfactant, an etherifying agent and a crosslinking agent, and carrying out heat preservation and stirring reaction to obtain slurry; the substitution degree of starch in the slurry is 0.1-0.3.
In the step (2), the invention can provide proper reaction environment and reaction power for starch and etherifying agent under the condition of specific pH value, catalyze and accelerate the etherification reaction, is more beneficial to maintaining higher etherification reaction efficiency of the starch in proper alkaline environment, and can not normally carry out the reaction to different degrees due to too high or too low reaction pH value, thus obtaining a product with proper etherification degree, and the recovery rate of wet starch products can bring larger influence. Meanwhile, the further etherification modification treatment is carried out, so that the comprehensive performance of the adhesive can be improved, and the functionality of the adhesive applied to the solidification type adhesive can be enhanced. In the invention, the anionic and/or nonionic etherification reaction is carried out under the alkaline condition of pH=10.0-12.0, the hydroxyl groups on starch molecules are utilized to carry out ionization reaction, then the added etherifying agent is attacked to carry out bimolecular nucleophilic substitution reaction, thus obtaining etherified modified starch products with different substitution degrees, generally, the comprehensive etherification degree after modification of the starch molecules is improved, the performance of starch is further improved, the problems of hardness, smearing performance, high temperature resistance, alkali resistance and the like of the modified starch materials in the later application process are greatly positively improved, and the best substitution degree of the starch-based materials is finally determined between 0.1 and 0.3 in combination with the application quality state requirement of the solidification type adhesive. If the substitution degree is lower, the bonding effect of the adhesive is poor, and if the substitution degree is too high, the expansion degree of the modified starch is deepened and becomes larger, the consistency and the expansion performance are improved, the fluidity is greatly reduced in the preparation process of the solidification type adhesive, the adhesive is not beneficial to glue filling, and the starch-based material with proper cost and higher starch yield, high temperature resistance and high alkaline energy is obtained.
(3) The pH value of the slurry is regulated to be 1.0-1.5 by acid, then an oxidant is added for oxidation reaction, and then an alkaline regulator is added for regulating the pH value to be 4.3-4.7, and the reaction is finished.
In the step (3), the pH of the slurry is firstly adjusted to 1.0-1.5, then an oxidant is added for acidolysis and oxidization treatment, the pH value is controlled to be 1.0-1.5 by the control process, the effect of controllably oxidatively degrading starch by the oxidant under the condition can be achieved, the molecular polymerization degree of the starch material can be reduced, and a new material with proper polymerization degree and containing a certain amount of carboxyl, aldehyde groups and other groups can be obtained. Specifically, the modified structure with acidification and oxidation commonality and the required performance modified product can be obtained more quickly by introducing oxidation treatment while acidifying under acidic conditions to reduce the polymerization degree of starch. The modified starch containing a certain amount of aldehyde groups, carbon groups and carboxyl groups is obtained by acidizing and oxidizing combination to treat starch, and the ageing and retrogradation characteristics of the starch modified molecule are improved while the polymerization degree of the starch molecule is reduced, so that the retrogradation gel with higher hardness can be formed in the preparation process of the solidification type adhesive, and conditions are created for strengthening the smearing performance, cohesiveness and optimizing the hardness index in the later period when the modified starch is specifically applied to the solidification type adhesive.
(4) Filtering and washing the product obtained in the step (3) to obtain refined pulp, adding the composite property improver, mixing and stirring, dehydrating, drying and sieving to obtain the starch-based material for the adhesive.
In the step (4), by further compounding the composite property improver, negative effects caused by digestion substances such as protein, lipid and the like in application of modified starch or other materials can be effectively stopped, chain reaction is avoided in the oxidation treatment process of grease and the like, adverse consequences such as color change and the like caused by long-time high-alkalinity conditions at high temperature are avoided, so that the property of the starch modified material under the conditions of long-time high temperature and high alkalinity is further improved, and the state stability of the adhesive is maintained.
Preferably, in the step (1), the starch is used in an amount of 1000 parts by weight, the water is used in an amount of 1200-160 parts by weight, more preferably 1200-1400 parts by weight, and the magnesium salt is used in an amount of 1.5-2.5 parts by weight.
Preferably, in the step (1), the starch is sorghum starch having a branched chain content of 95% or more. The alkaline regulator is a solution containing at least one of sodium hydroxide, sodium metaaluminate, potassium hydroxide and sodium silicate and having a weight percentage of 3-7%; the magnesium salt is magnesium sulfate.
Preferably, in the step (1), the temperature is raised to 45-55 ℃, and the reaction is carried out for 18-30 hours with heat preservation and stirring. It is further preferable to raise the temperature to 48-52 ℃, and the reaction is carried out for 20-22 hours with stirring at a constant temperature.
Preferably, in the step (2), the amount of the antigelling agent is 110 to 130 parts by weight, the amount of the surfactant is 0.01 to 0.05 part by weight, the amount of the etherifying agent is 120 to 150 parts by weight, and the amount of the crosslinking agent is 0.02 to 0.05 part by weight.
Preferably, in the step (2), the antigelling agent includes one or more of sodium sulfate, sodium chloride, sodium nitrate, and sodium phosphate; the surfactant is long-chain fatty alcohol polyoxyethylene ether; the etherifying agent comprises one or two of ethylene oxide, sodium chloroacetate, N- (2, 3-epoxypropyl) trimethyl ammonium chloride (GTA) and propylene oxide; the crosslinking agent comprises one or more of sodium trimetaphosphate, phosphorus oxychloride and epichlorohydrin.
Preferably, in the step (2), the time of the incubation reaction is 18-30 hours. Further preferably 20 to 22 hours.
Preferably, in the step (2), the etherifying agent includes two of ethylene oxide, sodium chloroacetate, N- (2, 3-epoxypropyl) trimethylammonium chloride (GTA) and propylene oxide.
Preferably, in the step (3), the amount of the oxidizing agent is 12 to 15 parts by weight; the oxidant is sodium periodate.
Preferably, in step (3), the pH of the slurry is adjusted to 1.2-1.4 with an acid; the oxidation reaction time is 1-3h.
Preferably, in the step (4), the compound performance improver is used in an amount of 1.0-3.0 parts by weight and comprises catalase, L-tryptophan and 2, 6-p-di-tert-butyl-p-cresol in a mass ratio of (0.03-0.05) to 1 to (6-10).
Preferably, in the step (4), the mixing and stirring time is 20-40min.
The starch-based material obtained by the preparation method can be used for preparing a solidification type adhesive. Compared with the prior art, the invention has the following technical effects: the invention provides a new starch modification route (wet heat treatment of starch, etherification, acidolysis and oxidization, addition of a composite property improver), and the obtained starch-based material has the characteristics of excellent smearing performance, good cohesiveness, high hardness, high temperature resistance, alkali resistance and the like after modifying and recombining molecular groups of starch.
Detailed Description
The invention is further described below with reference to examples.
General examples
The preparation method of the starch-based material for the adhesive comprises the following steps:
(1) 1000 parts by weight of starch (preferably sorghum starch with a branched chain content of more than 95%) and 1200-1600 parts by weight of water (preferably 1200-1400 parts by weight) are mixed and stirred into a slurry, an alkaline regulator (3-7 wt% sodium hydroxide, sodium metaaluminate, potassium hydroxide or sodium silicate solution) is added to adjust the pH value to 6.8-7.2, then 1.5-2.5 parts by weight of magnesium salt (preferably magnesium sulfate) is added, the temperature is raised to 45-55 ℃ (preferably 48-52 ℃), and the reaction is carried out for 18-30 hours (preferably 20-22 hours) with heat preservation and stirring.
(2) Adding an alkaline regulator (3-7wt% of sodium hydroxide, sodium metaaluminate, potassium hydroxide or sodium silicate solution) to regulate the pH value to 10.0-12.0, adding 110-130 parts by weight of an antigelling agent (preferably sodium sulfate, sodium chloride, sodium nitrate and sodium phosphate), 0.01-0.05 part by weight of a surfactant (preferably long-chain fatty alcohol polyoxyethylene ether), 120-150 parts by weight of an etherifying agent (preferably ethylene oxide, sodium chloroacetate, N- (2, 3-epoxypropyl) trimethylammonium chloride (GTA) and propylene oxide, further preferably two of ethylene oxide, sodium chloroacetate, N- (2, 3-epoxypropyl) trimethylammonium chloride (GTA) and propylene oxide) and 0.02-0.05 part by weight of a cross-linking agent (preferably sodium trimetaphosphate, phosphorus oxychloride and propylene oxide), and carrying out heat preservation stirring reaction for 18-30 hours (preferably 20-22 hours) to obtain slurry; the substitution degree of starch in the slurry is 0.1-0.3.
(3) The pH value of the slurry is adjusted to be 1.0-1.5 (preferably 1.2-1.4) by acid, 12-15 parts by weight of oxidant (preferably sodium periodate) is added to carry out oxidation reaction for 1-3 hours, then an alkaline regulator (3-7 wt% of sodium hydroxide, sodium metaaluminate, potassium hydroxide or sodium silicate solution) is added to adjust the pH value to be 4.3-4.7, and the reaction is finished.
(4) Filtering and washing the product obtained in the step (3) to obtain refined pulp, adding 1.0-3.0 parts by weight of a composite performance improver (preferably comprising catalase, L-tryptophan and 2, 6-p-di-tert-butyl-p-cresol according to the mass ratio of (0.03-0.05) to 1) to (6-10) into the refined pulp, mixing and stirring for 20-40min, dehydrating, drying and sieving to obtain the starch-based material for the adhesive.
Example 1
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complexing property modifier (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch base packaging material is obtained after dehydration and drying.
Example 2
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1400 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 3
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 11.8, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 4
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.05 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 5
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 150 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complexing property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 6
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 150 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:12 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 7
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.05 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complexing property improver (catalase, L-tryptophan and (2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 8
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 30h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixed slurry is stirred for 30min, and the mixed and sieved, and dried, and the starch-based material is obtained after drying.
Example 9
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.4, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 10
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 15 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Example 11
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for reaction for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 3h, finally, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complexing property modifier (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing is washed, the mixed, stirred, sieved and dried to obtain starch-based packaging material after dehydration and drying.
Example 12
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 3.0 g of composite property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Comparative example 1
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1750 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added and the temperature is raised to 50 ℃, the temperature is kept and stirred for reaction for 20h, then the pH value is adjusted to 10.5 by using 5wt% of potassium hydroxide aqueous solution, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent combined by sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction is kept for 20h to obtain reaction slurry, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is finished, 1.0 g of complexing property improver (catalase with the mass ratio of 0.04:1:8, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol) is added into the obtained refined slurry after rotary filtration and washing, the refined slurry is mixed and stirred for 30min, and dried to obtain the starch-based packaging material after dehydration and drying.
Comparative example 2
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 9.0, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Comparative example 3
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 200 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complexing property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Comparative example 4
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent combined by sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.2 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixed slurry is stirred for 30min, and the mixed and sieved, and dried, and the starch-based material is obtained after drying.
Comparative example 5
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 8 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complexing property modifier (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch base packaging material is obtained after dehydration and drying.
Comparative example 6
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 2.5, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5wt% of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 1.0 g of complex property improver (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is mixed and stirred for 30min, and dried, and the starch-based packaging material is obtained after dehydration and drying.
Comparative example 7
1000 g of raw material starch (sorghum starch with the concentration of more than 95%) and 1200 g of deionized water are stirred to form slurry, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 7.0, then 2 g of magnesium sulfate is added to heat up to 50 ℃, the temperature is kept and stirred for reaction for 20h, then 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 10.5, 120 g of sodium chloride, 0.02 g of fatty alcohol polyoxyethylene ether, 120 g of etherifying agent consisting of sodium chloroacetate and propylene oxide with the concentration of 1:15 and 0.02 g of epichlorohydrin are added, the reaction slurry is obtained after heat-keeping for 20h, 95 g of 15% hydrochloric acid is used to adjust the pH value to 1.2, 12 g of sodium periodate is added to carry out acidolysis with oxidation reaction for 1h, finally, 5 g of potassium hydroxide aqueous solution is added to adjust the pH value to 4.5, the reaction is ended, 5.0 g of complexing property modifier (catalase, L-tryptophan and 2, 6-p-di-tert-butyl p-cresol with the mass ratio of 0.04:1:8) is added to the refined slurry obtained after rotary filtration and washing, the mixture is stirred for 30min, and the product is dehydrated and dried, thus obtaining the starch-based packaging material.
Performance testing
The starch-based materials obtained in each of the examples and comparative examples were applied to the preparation of a setting adhesive (solid glue stick), respectively. Wherein: the formula comprises the following components: 45% of deionized water, 4% of maltose, 25% of starch-based material, 12% of propylene glycol methyl ether, 8% of PVP, 5.5% of sodium stearate, 0.2% of organosilicon defoamer, 0.3% of sodium benzoate, 0.05% of lemon essence and a proper amount of alkali liquor.
The preparation process comprises the following steps: under the stirring condition, adding deionized water, maltose, starch-based material, propylene glycol methyl ether and PVP in a beaker in sequence, standing for 1h after dispersing, stirring again, heating to 85 ℃, keeping the temperature, stirring for 2h, finally adding sodium stearate, lemon essence and alkali liquor, regulating the pH value to 10.6, keeping the temperature, defoaming for 20h, and pouring the glue and cooling to obtain the solidification type adhesive.
Performing experimental evaluation on each obtained solidified adhesive sample, wherein the evaluation of 1-10 minutes is given by combining the glue filling condition with the color and the smearing property of the adhesive, and the higher the score is, the better the overall performance and the quality of the adhesive are; hardness, adhesive strength were evaluated with reference to QB/T2857-2007.
Color score: 1-3 are divided into differences, 3-5 are divided into good, 5-8 are preferable, and 8-10 are preferable.
The spreadability score: 1-3 are divided into differences, 3-5 are divided into good, 5-8-good, and 8-10 are preferable.
Hardness score (fruit durometer, small tester): the data values are classified into four different grades, wherein the data is in a range of 2.0-2.5, the data is in a range of 2.5-3.0, the data is in a normal range, the data is in a range of 3.0-3.5, and the data is in a range of 3.5-4.0.
Adhesive strength score (performed with reference to QB/T2857-2007, using an HP-DL-Z paper strength tester): four different classes are used according to the data values, wherein the data is in the range of 8.0-9.5, the range of 9.5-11.5 is normal, the range of 11.5-13.5 is good, and the range of 13.5-16.0 is good.
The process differences and properties of the glue sticks obtained in examples 1-12 and comparative examples 1-7 are shown in the following table:
the specific scores of the glue sticks are shown in the following table:
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as can be seen from the comparison of the above table data, compared with the examples:
example 2 the reduction in the efficiency of the reactive etherification oxidation occurs as a result of the change in the powder-water ratio from 1:1.2 to 1:1.4, with the result that the color of the cured glue stick begins to deteriorate but is still within acceptable limits.
Example 3 the etherification efficiency is greatly improved due to the change of the pH value of the etherification reaction from 10.5 to 11.8, and the color of the solidified glue stick is improved to a certain extent as a result in application.
Example 4 an increase in surfactant from 0.02 g to 0.05 g resulted in a slight decrease in stick color, but increased foam levels in the application, resulting in increased difficulty in defoaming, but still in acceptable range.
Example 5 the etherifying agent was changed from 120 g 1:15 sodium chloroacetate and propylene oxide to 150 g sodium chloroacetate and propylene oxide and showed a slight decrease in the color of the gum stick in application, but a significantly better hardness.
Example 6 the etherifying agent is changed from 120 g of sodium chloroacetate and propylene oxide in a ratio of 1:15 to 150 g of sodium chloroacetate and propylene oxide in a ratio of 1:12, and compared with the prior art, the preparation of the glue is easier, and the later-stage glue has better and more transparent color.
In example 7, the cross-linking agent is changed from 0.02 g to 0.05 g, and the hardness of the glue stick is improved to a certain extent but the consistency of the glue solution is increased, and the later glue filling difficulty is increased but still in a qualified range.
In example 8, the etherification reaction time is prolonged from 20 hours to 30 hours, and the modified paste is obviously brighter, the reaction efficiency of the whole etherification, oxidization and crosslinking is increased, and the hardness is also increased to a certain extent, but the prolonged reaction time is also found to increase the water-soluble substances of the modified starch, so that the yield of the starch in the later period is slightly reduced.
Example 9 the acidolysis oxidation reaction pH was changed from 1.2 to 1.4 and a slight decrease in the viscosity of the colloid was found, because the pH was increased to result in insufficient acidolysis oxidation depth, resulting in a decrease in the cohesive part, but was still in the acceptable range.
Example 10 changed from 12 grams of oxidizer to 15 grams, and the result showed an increased oxidation level, slightly reduced viscosity, moderately increased hardness, better flowability and a partial reduction in color.
Example 11 changed the oxidation reaction time from 1h to 3h, resulting in a deepened oxidation degree, a slightly lowered viscosity, a partially raised hardness, and a slightly lowered color.
Example 12 the composite property improver was changed from 1.0 g to 3.0 g, and it was found that the color was more stable and the adhesive property was suitably improved.
In comparative examples 1 to 3, the ratio of the powder to the water was changed from 1:1.2 to 1:1.75, the pH value of the etherification reaction was reduced to 9.0, and the etherification agent was changed from 120 g to 200 g, which resulted in significant reduction in the reaction efficiency, deterioration of the color, yellowing, reduction of the cohesiveness, and finally, failure judgment.
The comparative example 4 changed the crosslinking agent from 0.02 g to 0.2 g, found that the color and luster was significantly reduced with the continuous increase of the crosslinking degree, and the coating property, hardness and bonding strength were reduced, probably because of the increase of the crosslinking, the swelling property of the starch was strongly inhibited, the overall performance was reduced, and finally the product was judged as unacceptable.
In comparative example 5, the oxidation agent was changed from 12 g to 8 g, which resulted in insufficient reduction of the molecular polymerization degree of the modified product, and the color and luster also significantly reduced off-yellow, and in particular, the smearing property, hardness and bonding strength were poor, and finally, the modified product was judged as unacceptable.
Comparative example 6 was changed from 1.2 to 2.5, and the oxidation reaction was accompanied by acid hydrolysis synergy to significantly reduce the molecular polymerization degree, and the result was substantially the same as comparative example 5, and finally, it was judged as being unacceptable.
The comparative example 7 changed the composite property improver from 1 g to 5 g, and the result was that the color was significantly reduced, and the application property, hardness and adhesive strength were also severely reduced, due to the large increase of the composite property improver, and finally judged as unacceptable.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the starch-based material for the adhesive is characterized by comprising the following steps of:
(1) Mixing 1000 parts by weight of starch and 1200-160 parts by weight of water, stirring to form slurry, adding an alkaline regulator to adjust the pH value to 6.8-7.2, then adding 1.5-2.5 parts by weight of magnesium salt, heating, preserving heat, and stirring for reaction;
(2) Adding an alkaline regulator to adjust the pH value to 10.0-12.0, adding 110-130 parts by weight of an antigelling agent, 0.01-0.05 part by weight of a surfactant, 120-150 parts by weight of an etherifying agent and 0.02-0.05 part by weight of a cross-linking agent, and carrying out heat preservation and stirring reaction to obtain slurry; the substitution degree of starch in the slurry is 0.1-0.3;
(3) Adjusting the pH value of the slurry to 1.0-1.5 by acid, adding 12-15 parts by weight of oxidant for oxidation reaction, adding alkaline regulator for adjusting the pH value to 4.3-4.7, and ending the reaction;
(4) Filtering and washing the product obtained in the step (3) to obtain refined pulp, adding 1.0-3.0 parts by weight of composite property improver, mixing and stirring, dehydrating, drying and sieving to obtain the starch-based material for the adhesive; the composite property improver comprises catalase, L-tryptophan and 2, 6-di-tert-butyl-p-cresol with the mass ratio of (0.03-0.05) being 1 (6-10).
2. The method of manufacturing according to claim 1, wherein: in the step (1), the step of (a),
the starch is sorghum starch with the branched chain content of more than 95%;
the magnesium salt is magnesium sulfate.
3. The preparation method according to claim 1 or 2, characterized in that: in the step (1), the temperature is raised to 45-55 ℃, and the reaction is carried out for 18-30h with heat preservation and stirring.
4. The method of manufacturing according to claim 1, wherein: in the step (2), the antigelling agent comprises one or more of sodium sulfate, sodium chloride, sodium nitrate and sodium phosphate;
the surfactant is fatty alcohol polyoxyethylene ether;
the etherifying agent comprises one or two of ethylene oxide, sodium chloroacetate, N- (2, 3-epoxypropyl) trimethyl ammonium chloride and propylene oxide;
the crosslinking agent comprises one or more of sodium trimetaphosphate, phosphorus oxychloride and epichlorohydrin.
5. The method of claim 1 or 4, wherein: in the step (2), the reaction time of heat preservation is 18-30h.
6. The method of manufacturing according to claim 4, wherein: in the step (2), the etherifying agent comprises two of ethylene oxide, sodium chloroacetate, N- (2, 3-epoxypropyl) trimethyl ammonium chloride and propylene oxide.
7. The method of manufacturing according to claim 1, wherein: in the step (3), the oxidant is sodium periodate.
8. The method of claim 1 or 7, wherein: in the step (3), the step of (c),
adjusting the pH of the slurry to 1.2-1.4 with an acid;
the oxidation reaction time is 1-3h.
9. The method of manufacturing according to claim 1, wherein: in the step (4), the step of (c),
the mixing and stirring time is 20-40min.
10. Use of a starch-based material obtained by the preparation method according to one of claims 1 to 9 for the preparation of a setting adhesive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101760149A (en) * | 2009-12-29 | 2010-06-30 | 莫元烈 | Environmental-friendly amylopectin composite adhesive for paper products and production method thereof |
| CN108314975A (en) * | 2018-02-08 | 2018-07-24 | 成都科创城科技有限公司 | A kind of preparation method of environment-friendly adhesive |
| CN114591446A (en) * | 2021-12-31 | 2022-06-07 | 杭州纸友科技有限公司 | Preparation method and application of modified starch polysaccharide derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101760149A (en) * | 2009-12-29 | 2010-06-30 | 莫元烈 | Environmental-friendly amylopectin composite adhesive for paper products and production method thereof |
| CN108314975A (en) * | 2018-02-08 | 2018-07-24 | 成都科创城科技有限公司 | A kind of preparation method of environment-friendly adhesive |
| CN114591446A (en) * | 2021-12-31 | 2022-06-07 | 杭州纸友科技有限公司 | Preparation method and application of modified starch polysaccharide derivative |
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