CN110804405A - Oxidized corn starch adhesive and preparation method thereof - Google Patents
Oxidized corn starch adhesive and preparation method thereof Download PDFInfo
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- CN110804405A CN110804405A CN201911143345.1A CN201911143345A CN110804405A CN 110804405 A CN110804405 A CN 110804405A CN 201911143345 A CN201911143345 A CN 201911143345A CN 110804405 A CN110804405 A CN 110804405A
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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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
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses an oxidized corn starch adhesive and a preparation method thereof, wherein the oxidized corn starch adhesive comprises the following steps: the oxidized corn starch adhesive comprises the following raw materials in parts by weight: 8-30 parts of corn starch, 0.9-2.0 parts of NaOH0.9 and H2O21 to 3 parts, 60 to 80 parts of water, 0.01 to 0.12 part of catalyst, 0.01 to 0.20 part of surfactant, 0.02 to 0.20 part of polyacrylamide, 0.1 to 2 parts of cross-linking agent, 0.1 to 1 part of diluent, 0.01 to 0.1 part of defoaming agent, 0.1 to 5 parts of drier, 0.01 to E0.5 part. The invention obtains the oxidized corn starch adhesive by pre-gelatinizing, oxidizing, gelatinizing, crosslinking and modifying the corn starch; the prepared oxidized corn starch adhesive has the advantages of good mechanical property, large initial adhesion, strong adhesion, high drying speed, good film forming property and good stability.
Description
Technical Field
The invention belongs to the technical field of application type fine chemical engineering, relates to the field of starch adhesives, and particularly relates to an oxidized corn starch adhesive and a preparation method thereof.
Background
The corn starch is a green and environment-friendly renewable natural product, is cheap and easy to obtain, and has good degradability. The corn starch adhesive is widely applied to the industries of paper making, building, printing and binding, medical treatment, carton packaging and bonding and the like. However, the conventional corn starch adhesive has the defects of unstable quality, low bonding force, poor fluidity, low drying speed and the like. The traditional method has the advantages of small expansion degree of starch granules, incomplete oxidation, relatively small number of generated carboxyl groups and low binding power. Probably because the gelatinized and expanded starch molecules are rearranged and combined to form a substance similar to starch macromolecules, the aging and gelatinization phenomena occur, and the stability is poor. In the cross-linking process of the traditional starch adhesive, hydroxyl in oxidized starch and empty orbitals of electrons at the outermost layer of boron atoms in a cross-linking agent form a network structure ligand, so that the starch adhesive becomes thick and poor in fluidity. The solid content is relatively low, so that the starch glue has poor water loss rate and low drying speed.
In conclusion, the research and development of the novel oxidized starch paste adhesive with good mechanical property, strong viscosity, quick drying and stability has wide significance.
Disclosure of Invention
The invention aims to provide an oxidized corn starch adhesive and a preparation method thereof, so as to solve one or more technical problems. The invention obtains the oxidized corn starch adhesive by pre-gelatinizing, oxidizing, gelatinizing, crosslinking and modifying the corn starch; the prepared oxidized corn starch adhesive has the advantages of good mechanical property, large initial adhesion, strong adhesion, high drying speed, good film forming property and good stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to an oxidized corn starch adhesive, which comprises the following raw materials in parts by weight: 8-30 parts of corn starch, 0.9-2.0 parts of NaOH0.9 and H2O21-3 parts of water, 60-80 parts of catalyst, 0.01-0.12 part of catalyst, 0.01-0.20 part of surfactant, 0.02-0.20 part of polyacrylamide, 0.1-2 parts of cross-linking agent, 0.1-1 part of diluent, 0.01-0.1 part of defoaming agent, 0.1-5 parts of drier and 0.01-0.5 part of preservative.
The invention further improves that the defoaming agent is tributyl phosphate, higher alcohol, aliphatic amide, polysiloxane, natural grease or glycerol.
In a further improvement of the invention, the diluent is one or more of urea, thiourea and boric acid; the cross-linking agent is borax, sodium metaborate, sodium trimetaphosphate or oxalic acid.
The invention is further improved in that the surfactant is one or more of sodium fatty acid, sodium higher fatty acid, fatty alcohol-polyoxyethylene ether sulfate and sodium pyrophosphate; the drier is one or more of polyvinyl alcohol, calcium carbonate, kaolin and sodium bentonite; the antiseptic is sodium benzoate, acrylic acid, calcium propionate, sodium sulfite, chlorinated hydrocarbon or p-hydroxybenzoate.
The preparation method of the oxidized corn starch adhesive sequentially comprises the following steps of:
1) weighing the raw materials according to the proportion; dividing the water into two parts, wherein one part is used for dissolving corn starch, and the other part is used for dissolving the rest other raw materials;
2) adding corn starch into a reactor, adding water, stirring until a uniform milky suspension is formed, adding a catalyst, heating, stirring for 15-40 min, and pre-gelatinizing;
3) adding H after pre-gelatinization2O2Dropwise adding NaOH while stirring to adjust the pH value to 8-10, heating and stirring for 1-2 h for oxidation;
4) after oxidation, adding the residual NaOH, stirring for 15-40 min, and pasting;
5) after pasting, adding a cross-linking agent, heating and stirring for cross-linking;
6) and after crosslinking, adding polyacrylamide, stirring for 5-15 min, sequentially adding a defoaming agent, a diluent, a surfactant, a drier and a preservative, continuously stirring for 20-40 min for modification, cooling and discharging to obtain the oxidized corn starch adhesive.
The further improvement of the invention is that in the step 2), the mixture is heated and stirred for 20-30 min, the heating temperature is 35-45 ℃, and the catalyst is ferrous sulfate.
In a further development of the invention, in step 3), H2O230 percent by mass, and is heated and stirred for 1-2 hours at a heating temperature of 55 &70℃。
The further improvement of the invention is that in the step 4), the heating and stirring are carried out for 25-30 min, and the gelatinization temperature is 55-65 ℃.
The further improvement of the invention is that in the step 5), the mixture is heated and stirred for 20-40 min, and the crosslinking temperature is 55-65 ℃.
The invention is further improved in that the defoaming agent is tributyl phosphate, higher alcohol, aliphatic amide, polysiloxane, natural grease or glycerol; the cross-linking agent is borax, sodium metaborate, sodium trimetaphosphate or oxalic acid; the diluent is one or more of urea, thiourea and boric acid; the surfactant is one or more of sodium fatty acid, sodium higher fatty acid, sodium alkyl sulfate, sodium alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sulfate and sodium pyrophosphate; the drier is one or more of polyvinyl alcohol, calcium chloride, calcium carbonate, kaolin and sodium bentonite; the antiseptic is sodium benzoate, acrylic acid, calcium propionate, sodium sulfite, chlorinated hydrocarbon or p-hydroxybenzoate.
Compared with the prior art, the invention has the following beneficial effects:
the oxidized corn starch adhesive has the advantages of large initial adhesion, strong adhesion, high drying speed and good stability.
The preparation method can prepare the oxidized corn starch adhesive, and the oxidized corn starch adhesive has the advantages of large initial adhesion, strong adhesion, high drying speed and good stability; specifically, the catalyst is adopted and heated and stirred for 15-40 min, so that the swelling degree of the starch cluster is better, and the oxidation probability is increased; adopts green environment-friendly H2O2Heating and stirring for 1-2 h as an oxidant, wherein the oxidation degree of the corn starch is better, and the content of carboxyl is the largest, so that the adhesive force of the oxidized corn starch glue is increased; heating and stirring for 15-40 min by using NaOH as a pasting agent, wherein the pasting effect of the oxidized corn is good, and the solubility and the fluidity of the oxidized corn are good; the crosslinking reaction is carried out by adding the crosslinking agent, heating and stirring, the crosslinking degree is better, and the adhesive force is large; the addition of surfactant and drier can effectively prevent starch from being largeThe agglomeration of molecules can prevent the aging of the corn starch glue and enhance the stability of the adhesive; the flexibility and the initial adhesion of the corn starch glue can be enhanced by adding polyacrylamide; the toughness and the fluidity of the starch glue can be enhanced by adding the diluent; the drying speed can be improved by adding the drier, and the solid content is increased.
Further, in the invention, the mixture is heated and stirred for 20-30 min, the heating temperature is 35-45 ℃, and the catalyst is ferrous sulfate; heating and stirring the mixture at 35-45 ℃ for 15-30 min by taking ferrous sulfate as a catalyst, wherein the expansion degree of the starch cluster is optimal, so that the oxidation probability is increased; if the pre-gelatinization time is too short, the degree of swelling of the starch dough is reduced; the expansion of the starch cluster destroys the hydroxyl association in the starch macromolecules to a certain extent, so that the oxidation probability is increased, after pre-gelatinization, the next oxidation reaction is relatively thorough, and the number of generated carboxyl groups is increased.
Further, H2O2The mass fraction is 30%, and the heating and stirring are carried out for 1-2 h, wherein the heating temperature is 55-70 ℃. The invention adopts green environment-friendly H2O2Heating and stirring the mixture as an oxidant at the temperature of 55-70 ℃ for 1-2 h, wherein the oxidation degree of the corn starch is optimal, and the carboxyl content is maximum so that the adhesion of oxidized corn starch glue is increased; the oxidation time is too short, the oxidation is not thorough, and the number of generated carboxyl is insufficient; meanwhile, the dosage of the oxidant cannot be too much, the number of generated carboxyl groups is increased along with the increase of the reaction time, and the number of the carboxyl groups is not increased any more after a certain reaction time. Excessive oxidant easily causes excessive oxidation, so that macromolecular chains of starch are broken, hydroxymethyl is changed into aldehyde groups, intermolecular hydrogen bonding is reduced, and viscosity is reduced. The reaction temperature is too low, the catalyst and the oxidant cannot well permeate into the starch granules, the reaction speed is slow, the oxidation degree is not enough, and the carboxyl content is low; at too high a temperature, the reaction rate increases, but the starch granules become gelatinized and the penetration of the oxidizing agent into the starch granules decreases, while at too high a temperature H increases2O2The decomposition rate of (a) results in a decrease in the degree of oxidation.
Further, the invention is heated and stirred for 25-30 min, and the gelatinization temperature is 55-65 ℃. Heating and stirring the oxidized corn for 15-30 min at 55-65 ℃ by using NaOH as a pasting agent, wherein the pasting effect of the oxidized corn is optimal, the reaction time is short due to good solubility and fluidity, hydrogen bonds among starch molecules are not opened, and carboxyl groups still have no hydrophilicity. The gelatinization is not complete due to too low temperature, the initial viscosity is reduced, the temperature is too high, the quality guarantee period is shortened, and the gelation phenomenon is easy to occur. NaOH is added to form sodium salt with carboxyl in oxidized starch, so that the fluidity and the solubility of the starch glue are improved, the excessive NaOH causes the viscosity of the starch glue to be reduced, the generated foam is increased, and the corrosivity is increased.
Further, heating and stirring are carried out for 20-40 min, and the crosslinking temperature is 55-65 ℃. According to the invention, the crosslinking reaction is carried out by adding the crosslinking agent, heating and stirring at 55-65 ℃ for 20-40 min, so that the crosslinking degree is optimal and the adhesive force is high; insufficient crosslinking time, insufficient crosslinking degree, reduced initial adhesion, too long crosslinking time, reduced adhesion and reduced transparency. The starch adhesive has the advantages that the crosslinking agent is insufficient, the crosslinking degree is insufficient, the self-polymerization is caused due to the hydrogen bond action among starch molecules, the retrogradation phenomenon is caused, the initial viscosity is poor, the crosslinking agent is excessive, the excessive crosslinking is caused, large-mesh-structure macromolecular substances can be formed with the starch, the fluidity of the corn starch adhesive is poor, and the gelatinization is easy to form.
Furthermore, the surface active agent and the polyvinyl alcohol are added, so that the agglomeration of starch macromolecules can be effectively prevented, the corn starch glue can be prevented from aging, and the stability of the adhesive can be enhanced; the flexibility and the initial adhesion of the corn starch glue can be enhanced by adding polyacrylamide; the toughness and the fluidity of the starch glue can be enhanced by adding the diluent; the drying speed can be improved by adding the drier, and the solid content is increased.
Detailed Description
In order to make the purpose, technical effect and technical solution of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described below; it is to be understood that the described embodiments are only some of the embodiments of the present invention. Other embodiments, which can be derived by one of ordinary skill in the art from the disclosed embodiments without inventive faculty, are intended to be within the scope of the invention.
The oxidized corn starch adhesive provided by the embodiment of the invention comprises the following raw materials in parts by weight,
wherein the used defoaming agent is tributyl phosphate, higher alcohol, aliphatic amide, polysiloxane, natural oil or glycerol, and the like, and the used diluent is urea, thiourea, boric acid, and the like; the surfactant is one or more of sodium fatty acid, sodium higher fatty acid, fatty alcohol-polyoxyethylene ether sulfate or sodium pyrophosphate; the drier is one or more of polyvinyl alcohol, calcium carbonate, kaolin, sodium bentonite and the like; the antiseptic is selected from sodium benzoate, acrylic acid, calcium propionate, sodium sulfite, chlorinated hydrocarbons, parabens, etc.
The preparation method of the oxidized corn starch adhesive provided by the embodiment of the invention specifically comprises the following steps:
1) preparing the raw materials according to the proportion, wherein water is deionized water, one part of the raw materials is used for dissolving corn starch, and the other part of the raw materials is used for dissolving other raw materials.
2) Adding corn starch into a reactor, adding water, continuously stirring until a uniform milky suspension is formed, adding a catalyst, heating and stirring for 20-40 min, and performing pre-gelatinization.
3) After pregelatinization, H is added2O2And dropwise adding NaOH to adjust the pH to be 8-10 under continuous stirring, and heating and stirring for 1-2 h for oxidation.
4) And after oxidation, adding the rest NaOH, stirring for 25-40 min, and pasting.
5) After pasting, adding a cross-linking agent, and stirring for 20-40 min for cross-linking.
6) And after crosslinking, sequentially adding polyacrylamide, stirring for 5-15 min, sequentially adding a defoaming agent, a diluent, a surfactant, a drier and a preservative, and continuously stirring for 20-40 min for modification. Cooling and discharging to obtain the oxidized corn paste starch glue.
Wherein, the heating and stirring in the step 2) are carried out for 15-30 min, the heating temperature is 35-45 ℃, and the catalyst is ferrous sulfate.
Step 3) H2O2The mass fraction is 30%, the heating and stirring are carried out for 1.5-2 h, and the heating temperature is 55-70 ℃.
And 4) heating and stirring for 15-30 min, wherein the gelatinization temperature is 55-65 ℃.
And step 5) heating and stirring for 20-40 min, wherein the crosslinking temperature is 55-65 ℃, and the crosslinking agents are borax, sodium metaborate, sodium trimetaphosphate, oxalic acid and the like.
The defoaming agent used in the step 6) is tributyl phosphate, higher alcohol, aliphatic amide, polysiloxane, natural oil or glycerol, and the like, and the diluent is urea, thiourea, boric acid, and the like; the surfactant is one or more of sodium fatty acid, sodium higher fatty acid, sodium alkyl sulfate, sodium alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether sulfate or sodium pyrophosphate; the drier is one or more of polyvinyl alcohol, calcium chloride, calcium carbonate, kaolin, sodium bentonite and the like; the antiseptic is selected from sodium benzoate, acrylic acid, calcium propionate, sodium sulfite, chlorinated hydrocarbons, parabens, etc.
The preparation method of the embodiment of the invention adopts green environment-friendly H2O2As an oxidant, ferrous sulfate is used as a catalyst to oxidize the corn starch. The oxidized corn starch paste adhesive provided by the embodiment of the invention can effectively prevent the aggregation of starch macromolecules by adding the surfactant and the polyvinyl alcohol, prevent the aging of starch glue and enhance the stability of the adhesive. The oxidized corn starch paste adhesive disclosed by the embodiment of the invention enhances the flexibility and initial adhesion of starch glue by adding polyacrylamide. The oxidized corn starch paste adhesive of the embodiment of the invention enhances the toughness of starch glue by adding a diluent. The invention relates to an oxidized corn starch paste adhesiveThe drying speed is improved and the solid content is increased by adding the drier. The invention has the advantages of simple and easily obtained raw materials, environmental protection and no public nuisance. The oxidized corn starch paste adhesive is prepared from corn starch, NaOH and H2O2The catalyst, the surfactant, the polyacrylamide, the cross-linking agent, the drier, the diluent and the like are used as raw materials and are prepared by a series of chemical reactions such as pre-gelatinization, cross-linking, modification and the like. The oxidized corn paste adhesive provided by the invention has the advantages of strong initial viscosity, large adhesive force, good fluidity and good stability. And the oxidized corn paste adhesive has the advantages of simple and easy process, convenient production, environment-friendly raw materials and low price.
Example 1
The preparation method of the oxidized corn starch paste adhesive provided by the embodiment of the invention comprises the following specific steps:
the adhesive comprises the following raw materials in parts by weight: corn starch 15 weight portions, NaOH 1.25 weight portions, and H2O22.5 parts of water, 75 parts of ferrous sulfate catalyst, 0.03 part of surfactant, 0.05 part of polyacrylamide, 0.15 part of borax cross-linking agent, 0.25 part of urea diluent, 0.03 part of tributyl phosphate defoaming agent, 0.35 part of drier and 0.1 part of preservative.
Preparing raw materials according to the proportion, wherein 75 parts of water is used for dissolving corn starch by 50 parts, and 25 parts of water is used for dissolving NaOH.
Adding 15 parts of corn starch into a reactor, adding 50 parts of water, stirring until a uniform milky suspension is formed, adding 0.03 part of ferrous sulfate catalyst, heating to 40 ℃, continuing stirring for 20min, pre-gelatinizing, adding 2.5 parts of H2O22mL of a 6.25% NaOH solution (a 6.25% NaOH solution prepared from 1.25 parts of NaOH) was added dropwise with stirring to adjust the pH to 8, and the mixture was heated to 60 ℃ and stirred for 1.5 hours to oxidize the reaction mixture. And adding the rest NaOH solution after the oxidation is finished, stirring for 30min, and pasting. Adding 0.15 part of borax, stirring for 30min for crosslinking, then stirring 0.05 part of polyacrylamide for 10min, sequentially adding 0.03 part of tributyl phosphate, 0.25 part of urea, 0.05 part of sodium dodecyl benzene sulfonate, 0.3 part of polyvinyl alcohol, 0.05 part of calcium carbonate and 0.1 part of sodium benzoate, and continuously stirring for 30mAnd in is modified. Cooling and discharging to obtain the oxidized corn paste starch glue.
Example 2
The preparation method of the oxidized corn starch paste adhesive provided by the embodiment of the invention comprises the following specific steps:
the raw material composition and weight portion ratio of the adhesive are 15 portions of corn starch, 1.25 portions of NaOH and H2O22.5 parts of water, 75 parts of ferrous sulfate catalyst, 0.03 part of surfactant, 0.05 part of polyacrylamide, 0.15 part of sodium trimetaphosphate cross-linking agent, 0.25 part of urea diluent, 0.03 part of tributyl phosphate defoaming agent, 0.35 part of sodium bentonite drier and 0.1 part of acrylic acid preservative.
Preparing raw materials according to the proportion, wherein 75 parts of water is used for dissolving corn starch by 50 parts, and 25 parts of water is used for dissolving NaOH.
Adding 15 parts of corn starch into a reactor, adding 50 parts of water, stirring until a uniform milky suspension is formed, adding 0.03 part of ferrous sulfate catalyst, heating to 40 ℃, continuing stirring for 20min, and pre-gelatinizing at the stirring speed of 500-1000 r/min. 2.5 parts of H are added2O22.1mL of a 6.25% NaOH solution (a 6.25% NaOH solution prepared from 1.25 parts NaOH) was added dropwise to the mixture while stirring at a pH of 10, and the mixture was heated to 60 ℃ and stirred for 1.5 hours to effect oxidation. And adding the rest NaOH solution after the oxidation is finished, stirring for 30min, and pasting. Adding 0.15 part of sodium trimetaphosphate, stirring for 30min for crosslinking, then adding 0.05 part of polyacrylamide, stirring for 10min, sequentially adding 0.03 part of tributyl phosphate, 0.25 part of urea, 0.05 part of sodium dodecyl benzene sulfonate, 0.3 part of polyvinyl alcohol, 0.05 part of sodium bentonite and 0.1 part of acrylic acid, and continuously stirring for 30min for modification. Cooling and discharging to obtain the oxidized corn paste starch glue.
Example 3
The adhesive comprises the following raw materials of, by weight, 10 parts of corn starch, 0.9 part of NaOH and H2O21.5 parts, 80 parts of water, 0.03 part of ferrous sulfate catalyst, 0.03 part of surfactant, 0.1 part of polyacrylamide, 0.1 part of cross-linking agent, 0.1 part of diluent, 0.01 part of defoaming agent, 1.0 part of drier and 0.1 part of preservative.
The procedure is as in example 1, except that
Wherein the defoaming agent is natural grease; the diluent is urea, thiourea and boric acid; the surfactant is a mixture of sodium fatty acid, sodium higher fatty acid and fatty alcohol-polyoxyethylene ether sulfate; the drier is sodium bentonite; the preservative is acrylic acid.
Example 4
The adhesive consists of corn starch 20 weight portions, NaOH 1.5 weight portions, and H2O23 parts of water, 70 parts of ferrous sulfate catalyst, 0.12 part of surfactant, 0.10 part of polyacrylamide, 0.5 part of cross-linking agent, 0.1 part of diluent, 0.1 part of defoaming agent, 0.35 part of drier and 0.3 part of preservative.
The procedure is as in example 1, except that
Wherein the defoaming agent is glycerol; the cross-linking agent is a mixture of sodium metaborate and borax; the surfactant sodium higher fatty acid; the drier is a mixture of kaolin and sodium bentonite; the preservative is parabens.
Example 5
The adhesive consists of corn starch 20 weight portions, NaOH 1.5 weight portions, and H2O23 parts of water, 70 parts of ferrous sulfate catalyst, 0.12 part of surfactant, 0.12 part of polyacrylamide, 1.0 part of cross-linking agent, 0.5 part of diluent, 0.1 part of defoaming agent, 0.35 part of drier and 0.3 part of preservative.
The procedure is as in example 1, except that
Wherein the defoamer is an aliphatic amide; the cross-linking agent is sodium metaborate; the diluent is a mixture of urea and thiourea; the drier is a mixture of calcium carbonate and sodium bentonite.
Example 6
The raw material composition and weight portion ratio of the adhesive are that corn starch 25 portions, NaOH 1.7 portions, H2O23.3 parts of water, 65 parts of ferrous sulfate catalyst, 0.15 part of surfactant and 0.15 part of polyacrylamide1.2 parts of cross-linking agent, 1.0 part of diluent, 0.1 part of defoaming agent, 0.5 part of drier and 0.5 part of preservative.
The procedure is as in example 1, except that
Wherein the cross-linking agent is sodium trimetaphosphate; the diluent is the mixture of thiourea and boric acid; the surfactant sodium higher fatty acid; the drier is a mixture of calcium chloride and sodium bentonite; the preservative is parabens.
Comparative example 1
The procedure is as in example 1, except that no polyacrylamide, defoamer, drier, diluent and preservative are added.
Comparative example 2
The procedure is as in example 1, except that no antifoam, diluent and preservative are added.
Performance testing of the oxidized corn adhesives prepared in inventive examples 1-7 and comparative examples 1-2:
1) measurement of peeling force
The peeling force of the corn starch adhesive is tested by adopting a GB/T2792-1998 pressure-sensitive adhesive tape 180-degree peeling strength test method;
2) measurement of adhesive Strength
Under constant temperature and humidity, 0.02g of corn starch glue is uniformly coated on the surface of a paper strip with the size of 16cm multiplied by 1.5cm, then the paper strip is bonded with another paper strip with the same specification, the bonding length is fixed to be 10cm, and the bonding strength is measured by a paper force tensile machine after the paper strip is naturally dried;
3) stability determination
Respectively measuring the viscosity of the prepared corn starch glue before and after the prepared corn starch glue is placed for 24 hours, wherein the stability is expressed by taking the ratio of the front viscosity to the rear viscosity as the stability;
4) determination of drying Rate
Two paper strips (specification is 160mm multiplied by 20mm) are taken, an adhesive is uniformly coated on one paper strip, the two paper strips are bonded together, the bonding length is fixed to be 100mm, the water loss percentage of the bonded paper strips in a certain period of time is the drying speed of the adhesive, and the time taken for the paper strips to be constant in weight is the total drying time of the adhesive, so that the quick drying is expressed.
The test results are given in the following table:
it can be seen by comparing examples 1-6 with comparative examples 1-2 that examples 1-6 are superior to comparative examples 1-2 in terms of bond strength, peel force drying speed, and stability. The adhesive strength and peel strength properties of example 4 are better, indicating that the addition of borax and sodium metaborate significantly improves the adhesive strength, probably due to the synergistic effect of the two. Example 4 shows that the drier plays a critical role in the drying speed of the adhesive, i.e. the addition of kaolin and sodium bentonite significantly increases the drying speed, mainly due to the synergistic effect of kaolin and sodium bentonite. In comparative example 1, polyacrylamide, a defoaming agent, a drier, a diluent and a preservative were not added, so that adhesive strength, peeling force, stability and drying speed were poor; in comparative example 2, no antifoaming agent, diluent and preservative were added, and thus its stability and adhesion were not strong.
The oxidized corn paste starch glue has the advantages of simple process flow, large initial adhesion, strong adhesion, high drying speed and good stability.
Example 8
The oxidized corn starch adhesive provided by the embodiment of the invention comprises the following raw materials in parts by weight: corn starch 8 weight portions, NaHOH0.9 weight portions, and H2O21 part, 60 parts of water, 0.01 part of catalyst, 0.01 part of surfactant, 0.02 part of polyacrylamide, 0.1 part of cross-linking agent, 0.1 part of diluent, 0.01 part of defoaming agent, 0.1 part of drier and 0.01 part of preservative.
The defoaming agent is aliphatic amide. The diluent is a mixture of urea, thiourea and boric acid. The cross-linking agent is sodium trimetaphosphate.
The surfactant is a mixture of sodium fatty acid, sodium higher fatty acid, fatty alcohol-polyoxyethylene ether sulfate and sodium pyrophosphate. The drier is a mixture of polyvinyl alcohol, calcium carbonate, kaolin and sodium bentonite; the preservative is parabens.
Example 9
The oxidized corn starch adhesive provided by the embodiment of the invention comprises the following raw materials in parts by weight: 30 portions of corn starch, 2.0 portions of NaOH and H2O23 parts of water, 80 parts of catalyst, 0.12 part of surfactant, 0.20 part of polyacrylamide, 2 parts of cross-linking agent, 1 part of diluent, 0.1 part of defoaming agent, 5 parts of drier and 0.5 part of preservative.
The defoaming agent is polysiloxane. The diluent is a mixture of thiourea and boric acid. The cross-linking agent is oxalic acid.
The surfactant is a mixture of sodium fatty acid, sodium higher fatty acid and sodium pyrophosphate; the drier is a mixture of calcium carbonate, kaolin and sodium bentonite; the preservative is parabens.
Example 10
The preparation method of the oxidized corn starch adhesive provided by the embodiment of the invention sequentially comprises the following steps:
1) weighing the raw materials according to the proportion; dividing the water into two parts, wherein one part is used for dissolving corn starch, and the other part is used for dissolving the rest other raw materials;
2) adding corn starch into a reactor, adding water, stirring until a uniform milky suspension is formed, adding a catalyst, heating and stirring for 40min, and pre-gelatinizing;
3) adding H after pre-gelatinization2O2Dropwise adding NaOH while stirring to adjust the pH value to 8-10, heating and stirring for 2h for oxidation, wherein the heating temperature is 55 ℃;
4) after oxidation, adding the residual NaOH, stirring for 40min and pasting; the gelatinization temperature is 65 ℃;
5) after pasting, adding a cross-linking agent, heating and stirring for cross-linking; heating and stirring for 40min, wherein the crosslinking temperature is 65 ℃;
6) and after crosslinking, adding polyacrylamide, stirring for 15min, sequentially adding a defoaming agent, a diluent, a surfactant, a drier and a preservative, continuously stirring for 40min for modification, cooling and discharging to obtain the oxidized corn starch adhesive.
Example 11
The embodiment of the present invention differs from embodiment 10 only in that:
in the step 2), heating and stirring are carried out for 30min, the heating temperature is 35-45 ℃, and the catalyst is ferrous sulfate.
In step 3), H2O2The mass fraction is 30 percent, and the mixture is heated and stirred for 1 hour, and the heating temperature is 70 ℃.
In the step 4), heating and stirring are carried out for 30min, and the gelatinization temperature is 55 ℃.
In the step 5), the mixture is heated and stirred for 20min, and the crosslinking temperature is 55 ℃.
Example 12
The embodiment of the present invention differs from embodiment 10 only in that:
in the step 2), heating and stirring are carried out for 20min, the heating temperature is 35 ℃, and the catalyst is ferrous sulfate.
In the step 3), the mixture is heated and stirred for 1.5h, and the heating temperature is 60 ℃.
In the step 4), heating and stirring are carried out for 25min, and the gelatinization temperature is 60 ℃.
In the step 5), heating and stirring are carried out for 30min, and the crosslinking temperature is 60 ℃.
Example 13
The embodiment of the present invention differs from embodiment 10 only in that:
in the step 2), the mixture is heated and stirred for 10min, and the heating temperature is 30 ℃.
In the step 4), heating and stirring are carried out for 15-30 min, and the gelatinization temperature is 65 ℃.
Example 14
The preparation method of the oxidized corn starch adhesive provided by the embodiment of the invention sequentially comprises the following steps:
the preparation method sequentially comprises the following steps:
1) weighing the raw materials according to the proportion; dividing the water into two parts, wherein one part is used for dissolving corn starch, and the other part is used for dissolving the rest other raw materials;
2) adding corn starch into a reactor, adding water, stirring until a uniform milky suspension is formed, adding a catalyst, heating and stirring for 15min, and pre-gelatinizing;
3) adding H after pre-gelatinization2O2Dropwise adding NaOH while stirring to adjust the pH value to 8-10, heating and stirring for 1h for oxidation;
4) after oxidation, adding the residual NaOH, stirring for 15min and pasting;
5) after pasting, adding a cross-linking agent, heating and stirring for cross-linking;
6) and after crosslinking, adding polyacrylamide, stirring for 5min, sequentially adding a defoaming agent, a diluent, a surfactant, a drier and a preservative, continuously stirring for 20min for modification, cooling and discharging to obtain the oxidized corn starch adhesive.
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the embodiments of the present invention without departing from the spirit and scope of the present invention, which is set forth in the claims of the present application.
Claims (10)
1. An oxidized corn starch adhesive is characterized in that,
the oxidized corn starch adhesive comprises the following raw materials in parts by weight: 8-30 parts of corn starch, 0.9-2.0 parts of NaOH0.9 and H2O21-3 parts of water, 60-80 parts of catalyst, 0.01-0.12 part of catalyst, 0.01-0.20 part of surfactant, 0.02-0.20 part of polyacrylamide, 0.1-2 parts of cross-linking agent, 0.1-1 part of diluent, 0.01-0.1 part of defoaming agent, 0.1-5 parts of drier and 0.01-0.5 part of preservative.
2. The oxidized corn starch adhesive according to claim 1, wherein the antifoaming agent is tributyl phosphate, higher alcohols, fatty amides, silicones, natural oils or glycerol.
3. The oxidized corn starch adhesive of claim 1, wherein the diluent is one or more of urea, thiourea and boric acid;
the cross-linking agent is borax, sodium metaborate, sodium trimetaphosphate or oxalic acid.
4. The oxidized corn starch adhesive of claim 1, wherein the surfactant is one or more of sodium fatty acid, sodium higher fatty acid, fatty alcohol polyoxyethylene ether sulfate, and sodium pyrophosphate;
the drier is one or more of polyvinyl alcohol, calcium carbonate, kaolin and sodium bentonite;
the antiseptic is sodium benzoate, acrylic acid, calcium propionate, sodium sulfite, chlorinated hydrocarbon or p-hydroxybenzoate.
5. A method of preparing the oxidized corn starch adhesive of claim 1,
the preparation method sequentially comprises the following steps:
1) weighing the raw materials according to the proportion; dividing the water into two parts, wherein one part is used for dissolving corn starch, and the other part is used for dissolving the rest other raw materials;
2) adding corn starch into a reactor, adding water, stirring until a uniform milky suspension is formed, adding a catalyst, heating, stirring for 15-40 min, and pre-gelatinizing;
3) adding H after pre-gelatinization2O2Dropwise adding NaOH while stirring to adjust the pH value to 8-10, heating and stirring for 1-2 h for oxidation;
4) after oxidation, adding the residual NaOH, stirring for 15-40 min, and pasting;
5) after pasting, adding a cross-linking agent, heating and stirring for cross-linking;
6) and after crosslinking, adding polyacrylamide, stirring for 5-15 min, sequentially adding a defoaming agent, a diluent, a surfactant, a drier and a preservative, continuously stirring for 20-40 min for modification, cooling and discharging to obtain the oxidized corn starch adhesive.
6. The preparation method of the oxidized corn starch adhesive according to claim 5, wherein in the step 2), the mixture is heated and stirred for 20-30 min at a temperature of 35-45 ℃ and the catalyst is ferrous sulfate.
7. The method for preparing oxidized corn starch adhesive according to claim 5, wherein in step 3), H2O2The mass fraction is 30%, and the heating and stirring are carried out for 1-2 h, wherein the heating temperature is 55-70 ℃.
8. The preparation method of the oxidized corn starch adhesive according to claim 5, wherein in the step 4), the mixture is heated and stirred for 25-30 min, and the gelatinization temperature is 55-65 ℃.
9. The preparation method of the oxidized corn starch adhesive according to claim 5, wherein in the step 5), the mixture is heated and stirred for 20-40 min, and the crosslinking temperature is 55-65 ℃.
10. The method for preparing the oxidized corn starch adhesive according to claim 5, wherein the defoaming agent is tributyl phosphate, higher alcohol, aliphatic amide, polysiloxane, natural oil or glycerol;
the cross-linking agent is borax, sodium metaborate, sodium trimetaphosphate or oxalic acid;
the diluent is one or more of urea, thiourea and boric acid;
the surfactant is one or more of sodium fatty acid, sodium higher fatty acid, sodium alkyl sulfate, sodium alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sulfate and sodium pyrophosphate;
the drier is one or more of polyvinyl alcohol, calcium chloride, calcium carbonate, kaolin and sodium bentonite;
the antiseptic is sodium benzoate, acrylic acid, calcium propionate, sodium sulfite, chlorinated hydrocarbon or p-hydroxybenzoate.
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| CN114634777A (en) * | 2022-04-18 | 2022-06-17 | 北京纳威光合科技有限公司 | Starch adhesive, preparation method and application thereof |
| CN115490556A (en) * | 2022-10-27 | 2022-12-20 | 云南云叶化肥股份有限公司 | Auxiliary additive beneficial to fertilizer disc granulation and preparation method thereof |
| CN115678457A (en) * | 2022-11-22 | 2023-02-03 | 广西至善新材料科技有限公司 | Degradable adhesive and preparation method thereof |
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| CN115895505A (en) * | 2022-11-30 | 2023-04-04 | 汇胜包装科技有限公司 | Special starch glue for high-temperature-resistant drying paper tube and preparation method thereof |
| CN115895505B (en) * | 2022-11-30 | 2024-08-20 | 汇胜包装科技有限公司 | Special starch adhesive for high-temperature-resistant drying paper tube and preparation method thereof |
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