CN110551462A - environment-friendly high-viscosity weather-resistant modified starch adhesive and preparation method thereof - Google Patents
environment-friendly high-viscosity weather-resistant modified starch adhesive and preparation method thereof Download PDFInfo
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—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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- 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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- 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
- C09J11/08—Macromolecular additives
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Abstract
The invention discloses an environment-friendly high-viscosity weather-resistant modified starch adhesive and a preparation method thereof, wherein the adhesive comprises the following components in parts by weight: 20-30 parts of soluble starch; 50-70 parts of tertiary water; 0.1-1 part of polyvinyl alcohol; 1-10 parts of a pH regulator; 1-5 parts of a pasting agent; 2-8 parts of hydrogen peroxide; 0.1-1 part of carboxylic acid cross-linking agent; 0.5-2 parts of borax; 0.1-5 parts of an auxiliary agent. The adhesive is prepared by mixing polyvinyl alcohol, starch and tertiary water, adding hydrogen peroxide to oxidize under an alkaline environment, destroying hydrogen bonds of the starch to modify, adding a carboxylic acid cross-linking agent to cross-link to form a stable network structure, and then gelatinizing, complexing and dispersing to obtain the environment-friendly high-viscosity modified starch adhesive with the capabilities of resisting high temperature, high humidity, low temperature and high and low temperature cyclic impact.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an environment-friendly high-viscosity weather-resistant modified starch adhesive and a preparation method thereof.
background
The traditional adhesive is mainly prepared from resin and an organic solvent, volatile solvents harmful to human bodies can be generated in the processes of production, use and subsequent drying, and formaldehyde is also generated, so that the traditional adhesive is gradually replaced by a water-based adhesive, the water-based adhesive is environment-friendly compared with the traditional organic solvent-based adhesive, the main components of the water-based adhesive are mainly prepared from various resins and emulsions, the water-based adhesive is not really environment-friendly and non-renewable, and the solvent is water, so that the adhesive is easy to crack under the environment of high temperature and high humidity, and the quality of products is influenced. As starch is one of the main grain crops in China, has rich resources, wide sources, is natural, green, environment-friendly and renewable, most of the existing adhesives take starch as a main connecting material, the starch is heated and swelled to obtain gelatinized starch, the gelatinized starch obtained by the method contains a large amount of hydrogen bonds, so that the system has poor fluidity, high viscosity, easy caking and short storage time, the adhesive force is poor, the scale industrial application is not suitable, the problems of mildew, weak adhesive capacity, poor plasticizing effect and the like are caused, furthermore, the aldehyde-free adhesive prepared from the starch is often used for bonding paper boards, wood boards and the like, and sometimes the materials of the paper boards, the wood boards and the like are required to be used for containing high-temperature and low-temperature substances or used under severe conditions such as high-temperature and high-humidity, high-temperature and low-temperature cyclic impact and the like, however, the traditional starch adhesive has poor weather resistance and cannot meet the use requirements of severe conditions.
therefore, the inventors have endeavored to design an environment-friendly high-viscosity weather-resistant modified starch adhesive and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to: the environment-friendly high-viscosity weather-resistant modified starch adhesive is modified by breaking hydrogen bonds of starch, so that the adhesive force is increased, the storage time is prolonged, and meanwhile, groups generated after starch molecules are modified and added compounds are crosslinked to form a stable network structure, so that the adhesive has the capabilities of resisting high temperature, high humidity, low temperature and high and low temperature cyclic impact.
Another object of the present invention is to: the preparation method of the environment-friendly high-viscosity weather-resistant modified starch adhesive is provided, and the environment-friendly modified starch adhesive with strong adhesive force, high temperature and high humidity resistance, low temperature resistance and high and low temperature cycle impact resistance is prepared by destroying starch hydrogen bonds and forming a stable network structure by crosslinking with an added compound.
in order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the environment-friendly high-viscosity weather-resistant modified starch adhesive comprises the following components in parts by weight:
the tertiary water of the invention is prepared by a ultrapure water system PURIST UV.
The purity of the borax is analytically pure, not only plays a role of complexing, but also serves as a cross-linking agent for improving the cross-linking degree and initial viscosity of the starch adhesive, and the principle is as follows: the borax and the hydroxyl, carboxyl and the like of the gelatinized oxidized starch form a net structure with [ B4O7] 2-as the center in water, and the net structure has the functions of crosslinking and tackifying, thereby being beneficial to improving the initial adhesion, accelerating the adhesion speed, leading the adhesive film to be firm and enhancing the moisture resistance.
The principle of modification and crosslinking of the starch adhesive is as follows: under alkaline conditions, macromolecular starch is oxidized into micromolecular starch, and simultaneously carboxyl is generated, and under alkaline conditions, the carboxyl is crosslinked with hydroxyl on polyvinyl alcohol and hydroxyl on other starch molecules to form a stable covalent bond; the carboxyl of the carboxylic acid cross-linking agent is cross-linked with the oxidized starch molecules and the polyvinyl alcohol to generate a stable covalent bond; after the starch is gelatinized, boron atoms of the borax are crosslinked with gelatinized starch molecules and polyvinyl alcohol molecules through boron hydrogen bonds to form stable covalent bonds. Stable covalent bonds are formed through intermolecular crosslinking, and meanwhile, a plurality of covalent bonds are crosslinked with each other to form a stable network structure, so that the starch adhesive has the capability of resisting high-temperature, high-humidity and low-temperature environments.
The starch adhesive is a weather-resistant high-viscosity adhesive which is prepared by taking soluble starch as a raw material through a series of modification methods, the adhesive does not contain formaldehyde, the raw material is natural, green, environment-friendly and renewable, and the adhesive is a real environment-friendly adhesive.
The modified starch adhesive is an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, and comprises the following components in parts by weight:
as an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, the carboxylic acid cross-linking agent is dicarboxylic acid or polycarboxylic acid.
Dicarboxylic acids refer to carboxylic acids containing two carboxyl groups-COOH, and polycarboxylic acids refer to carboxylic acids containing three or more carboxyl groups-COOH.
As an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, the dicarboxylic acid is food-grade adipic acid.
the adipic acid can generate cross-linking with starch molecules in the solution and hydroxyl on polyvinyl alcohol to form a network chain structure, so that the viscosity of the adhesive is increased.
as an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, the mass fraction of the hydrogen peroxide is 29-32%.
In the preparation process of the adhesive, the hydrogen peroxide is used as an oxidant and is used for destroying oxygen bridges in starch molecules, one oxygen bridge is oxidized and broken, and starch molecules are depolymerized into two smaller molecules from one molecule and oxidized to generate carboxyl under the alkaline condition.
as an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, the polymerization degree of the polyvinyl alcohol is 1700-1800.
the polyvinyl alcohol is of experimental grade and serves to increase the viscosity and adhesion of the adhesive.
as an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, the auxiliary agent is at least one of a dispersing agent, a leveling wetting agent, a viscosity stabilizer and a defoaming agent;
The dispersing agent is potassium pyrophosphate, the purity of the potassium pyrophosphate is analytically pure, and the solution is uniformly dispersed;
the leveling wetting agent is Dow Corning DC-67 and is used for improving the fluidity of the adhesive;
The viscosity stabilizer is butanol or phenol, and the purity of the butanol is analytically pure;
the antifoaming agent is Dow Corning DC-65 silicone antifoaming agent.
Potassium pyrophosphate is also known as tetrapotassium pyrophosphate, white powder or bulk solid, with a relative density of 2.534, melting point of 1109 ℃, water solubility of 187g/100g water (25 ℃). The aqueous solution was alkaline, and the pH of the 1% aqueous solution was 10.2. Is insoluble in ethanol.
Butanol relative density (d2020)0.8109, boiling point 117.7 ℃, melting point-90.2 ℃, refractive index (n20D)1.3993, flash point 35-35.5 ℃, spontaneous ignition point 365 ℃, solubility in water at 20 ℃ 7.7% by weight, solubility in n-butanol 20.1% by weight.
Dow Corning DC-67 and Dow Corning DC-65 Silicone defoamers are both available from Dow Corning, USA.
As an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, the soluble starch is at least one of rice starch, corn starch, millet starch, potato starch, sweet potato starch, wheat starch and pea starch, and the purity of the soluble starch is analytically pure.
as an improvement of the environment-friendly high-viscosity weather-resistant modified starch adhesive, the PH regulator is a sodium hydroxide solution with the mass fraction of 2%, the pasting agent is a sodium hydroxide solution with the mass fraction of 30%, and the PH regulator and the pasting agent are both prepared from sodium hydroxide with the purity of analytical purity and tertiary water.
Because sodium hydroxide belongs to strong base, the pH value of the solution can be greatly changed by using less high-concentration sodium hydroxide, and the pH value of the solution cannot be controlled, therefore, the invention adopts low-concentration sodium hydroxide as a pH regulator, namely 2% sodium hydroxide, to regulate the pH value of the solution in the starch oxidation process, thereby providing a stable alkaline environment, and 30% sodium hydroxide is an additive in the starch gelatinization stage.
In order to achieve the other purpose, the invention adopts the technical scheme that:
the preparation method of the modified starch adhesive comprises the following steps:
S1, mixing: putting the three-necked bottle into a constant-temperature water bath kettle at 55-65 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 55-65 ℃, continuously stirring at the speed of 450-550 r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
s2, oxidation: adjusting the pH of the mixed solution to 9-10 by using a pH regulator, gradually adding hydrogen peroxide, adjusting the pH by using the pH regulator, keeping the pH in the mixed solution at 9-10, continuously oxidizing for 2.5-3 hours, oxidizing macromolecular starch into micromolecular starch under an alkaline condition, generating carboxyl, and crosslinking the carboxyl with hydroxyl on polyvinyl alcohol and hydroxyl on other starch molecules under the alkaline condition to form a stable covalent bond;
S3, crosslinking: adding a carboxylic acid cross-linking agent, keeping the temperature at 55-65 ℃, and stirring for 0.5-1.5 hours to enable carboxyl of the carboxylic acid cross-linking agent, oxidized starch molecules and polyvinyl alcohol to generate cross-linking to generate stable covalent bonds;
s4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
S5, complexing: adding borax, and stirring for 15-45 minutes to enable boron atoms of the borax to form stable covalent bonds through boron-hydrogen bonds and crosslinking with gelatinized starch molecules and polyvinyl alcohol molecules;
S6, dispersing: adding the auxiliary agent, stirring for 5-15 minutes, cooling, sealing and storing.
Compared with the prior art, the environment-friendly high-viscosity weather-resistant modified starch adhesive has the following technical effects: the starch raw material without formaldehyde is used to prepare a real environment-friendly adhesive, hydrogen bonds of the starch are broken to modify the adhesive, so that the viscosity of the adhesive is increased to 80-120 s (25 ℃), the storage time is prolonged, and meanwhile, groups generated after starch molecule modification and added compounds are crosslinked to form a stable network structure, so that the adhesive has the capabilities of resisting high temperature, high humidity, low temperature and high and low temperature cyclic impact, wherein the high and low temperature resistance ranges from-25 ℃ to 70 ℃, and the highest humidity is 96%.
the preparation method of the environment-friendly high-viscosity weather-resistant modified starch adhesive is simple, the stable network structure is formed by destroying the hydrogen bonds of the starch and crosslinking the starch with the added compound, the environment-friendly modified starch with strong adhesive force, high temperature and high humidity resistance, low temperature resistance and high and low temperature cycle impact resistance is prepared, the manufacturing cost is low, and the environment-friendly high-viscosity weather-resistant modified starch adhesive is suitable for large-scale industrial application.
Detailed Description
example 1
The embodiment provides an environment-friendly high-viscosity weather-resistant modified starch adhesive which comprises the following components in parts by weight:
Wherein the carboxylic acid cross-linking agent is dicarboxylic acid, namely food-grade adipic acid, the mass fraction of hydrogen peroxide is 29%, the polymerization degree of polyvinyl alcohol is 1700, the auxiliary agent is a mixture of potassium pyrophosphate, Dow Corning DC-67, butanol and Dow Corning DC-65 silicone defoamer, and the mass ratio of the four is 1: 1: 1: 1, the PH regulator is a sodium hydroxide solution with the mass fraction of 2%, the pasting agent is a sodium hydroxide solution with the mass fraction of 30%, and the PH regulator and the pasting agent are both prepared from sodium hydroxide with analytical purity and tertiary water.
The preparation method comprises the following steps:
s1, mixing: placing the three-necked bottle in a constant-temperature water bath kettle at 55 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 55 ℃, continuously stirring at the speed of 550r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
S2, oxidation: regulating the pH of the mixed solution to 9 by using a pH regulator, gradually adding hydrogen peroxide, regulating the pH by using the pH regulator simultaneously to keep the pH in the mixed solution at 9, and continuously oxidizing for 3 hours;
s3, crosslinking: adding a carboxylic acid cross-linking agent, maintaining the temperature at 55 ℃ and stirring for 1.5 hours;
S4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
s5, complexing: adding borax and stirring for 45 minutes;
s6, dispersing: adding the auxiliary agent, stirring for 15 minutes, cooling and storing in a sealing way.
Example 2
the embodiment provides an environment-friendly high-viscosity weather-resistant modified starch adhesive which comprises the following components in parts by weight:
wherein the carboxylic acid cross-linking agent is polycarboxylic acid, the mass fraction of hydrogen peroxide is 30%, the polymerization degree of polyvinyl alcohol is 1750, the auxiliary agent is a mixture of potassium pyrophosphate, Dow Corning DC-67, phenol and Dow Corning DC-65 silicone defoamer, and the mass ratio of the four is 2: 5: 5: 5, the PH regulator is a sodium hydroxide solution with the mass fraction of 2%, the pasting agent is a sodium hydroxide solution with the mass fraction of 30%, and the PH regulator and the pasting agent are both prepared from sodium hydroxide with analytical purity and tertiary water.
the preparation method comprises the following steps:
s1, mixing: placing the three-necked bottle in a constant temperature water bath kettle at 60 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 60 ℃, continuously stirring at the speed of 500r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
S2, oxidation: adjusting the pH of the mixed solution to 9.5 by using a pH regulator, gradually adding hydrogen peroxide, adjusting the pH by using the pH regulator simultaneously to keep the pH in the mixed solution between 9.5, and continuously oxidizing for 3 hours;
S3, crosslinking: adding a carboxylic acid cross-linking agent, maintaining the temperature at 60 ℃ and stirring for 1 hour;
s4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
S5, complexing: adding borax and stirring for 30 minutes;
S6, dispersing: adding the auxiliary agent, stirring for 10 minutes, cooling and storing in a sealing way.
Example 3
the embodiment provides an environment-friendly high-viscosity weather-resistant modified starch adhesive which comprises the following components in parts by weight:
Wherein the carboxylic acid cross-linking agent is food-grade adipic acid, the mass fraction of hydrogen peroxide is 30%, the polymerization degree of polyvinyl alcohol is 1750, the auxiliary agent is a mixture of potassium pyrophosphate, Dow Corning DC-67, butanol and Dow Corning DC-65 silicone defoamer, and the mass ratio of the four is 2: 5: 5: 5, the PH regulator is a sodium hydroxide solution with the mass fraction of 2%, the pasting agent is a sodium hydroxide solution with the mass fraction of 30%, and the PH regulator and the pasting agent are both prepared from analytically pure sodium hydroxide and tertiary water.
The preparation method comprises the following steps:
s1, mixing: placing the three-necked bottle in a constant temperature water bath kettle at 60 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 60 ℃, continuously stirring at the speed of 500r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
S2, oxidation: adjusting the pH of the mixed solution to 9 by using 2% sodium hydroxide, gradually adding hydrogen peroxide, adjusting the pH by using 2% sodium hydroxide simultaneously to keep the pH in the mixed solution at 9, and continuously oxidizing for 3 hours;
S3, crosslinking: adding a carboxylic acid cross-linking agent, maintaining the temperature at 60 ℃ and stirring for 1 hour;
s4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
s5, complexing: adding borax and stirring for 30 minutes;
S6, dispersing: adding the auxiliary agent, stirring for 10 minutes, cooling and storing in a sealing way.
example 4
The embodiment provides an environment-friendly high-viscosity weather-resistant modified starch adhesive which comprises the following components in parts by weight:
wherein the carboxylic acid cross-linking agent is food-grade adipic acid, the mass fraction of hydrogen peroxide is 30%, the polymerization degree of polyvinyl alcohol is 1750, the auxiliary agent is a mixture of potassium pyrophosphate, Dow Corning DC-67 and butanol, and the mass ratio of the three is 2: 5: 5, the PH regulator is a sodium hydroxide solution with the mass fraction of 2%, the pasting agent is a sodium hydroxide solution with the mass fraction of 30%, and the PH regulator and the pasting agent are both prepared from sodium hydroxide with analytical purity and tertiary water.
The preparation method comprises the following steps:
s1, mixing: placing the three-necked bottle in a constant-temperature water bath kettle at 63 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 63 ℃, continuously stirring at 460r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
s2, oxidation: regulating the pH of the mixed solution to 9.4 by using a pH regulator, gradually adding hydrogen peroxide, regulating the pH by using the pH regulator simultaneously to keep the pH in the mixed solution at 9.4, and continuously oxidizing for 2.6 hours;
S3, crosslinking: adding a carboxylic acid cross-linking agent, maintaining the temperature at 63 ℃ and stirring for 1 hour;
s4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
S5, complexing: adding borax and stirring for 35 minutes;
S6, dispersing: adding the auxiliary agent, stirring for 12 minutes, cooling and storing in a sealing way.
example 5
The embodiment provides an environment-friendly high-viscosity weather-resistant modified starch adhesive which comprises the following components in parts by weight:
Wherein the carboxylic acid cross-linking agent is food-grade adipic acid, the mass fraction of hydrogen peroxide is 31%, the polymerization degree of polyvinyl alcohol is 1755, the auxiliary agent is a mixture of potassium pyrophosphate, Dow Corning DC-67, butanol and Dow Corning DC-65 silicone defoamer, and the mass ratio of the four is 1: 1: 1: 1, the PH regulator is a sodium hydroxide solution with the mass fraction of 2%, the pasting agent is a sodium hydroxide solution with the mass fraction of 30%, and the PH regulator and the pasting agent are both prepared from sodium hydroxide with analytical purity and tertiary water.
The preparation method comprises the following steps:
S1, mixing: placing the three-necked bottle in a constant-temperature water bath kettle at 64 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 64 ℃, continuously stirring at 530r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
s2, oxidation: regulating the pH of the mixed solution to 10 by using a pH regulator, gradually adding hydrogen peroxide, regulating the pH by using the pH regulator simultaneously to keep the pH in the mixed solution at 10, and continuously oxidizing for 2.5 hours;
S3, crosslinking: adding a carboxylic acid cross-linking agent, maintaining the temperature at 64 ℃ and stirring for 0.5 hour;
s4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
S5, complexing: adding borax, and stirring for 20 minutes;
S6, dispersing: adding the auxiliary agent, stirring for 10 minutes, cooling and storing in a sealing way.
Example 6
The embodiment provides an environment-friendly high-viscosity weather-resistant modified starch adhesive which comprises the following components in parts by weight:
Wherein the carboxylic acid cross-linking agent is food-grade adipic acid, the mass fraction of hydrogen peroxide is 32%, the polymerization degree of polyvinyl alcohol is 1800, the auxiliary agent is a mixture of potassium pyrophosphate, Dow Corning DC-67, butanol and Dow Corning DC-65 silicone defoamer, and the mass ratio of the four is 1: 2: 2: 2, the PH regulator is a sodium hydroxide solution with the mass fraction of 2%, the pasting agent is a sodium hydroxide solution with the mass fraction of 30%, and the PH regulator and the pasting agent are both prepared from sodium hydroxide with analytical purity and tertiary water.
the preparation method comprises the following steps:
s1, mixing: putting the three-necked bottle into a constant-temperature water bath kettle at 65 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 65 ℃, continuously stirring at the speed of 450r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
s2, oxidation: regulating the pH of the mixed solution to 10 by using a pH regulator, gradually adding hydrogen peroxide, regulating the pH by using the pH regulator simultaneously to keep the pH in the mixed solution at 10, and continuously oxidizing for 2.5 hours;
S3, crosslinking: adding a carboxylic acid cross-linking agent, keeping the temperature at 65 ℃ and stirring for 0.5 hour;
S4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
S5, complexing: adding borax and stirring for 15 minutes;
s6, dispersing: adding the auxiliary agent, stirring for 5 minutes, cooling and storing in a sealing way.
since the adhesive property of the adhesive is characterized by the initial adhesion, the modified starch adhesive prepared in 6 examples of the invention is subjected to the initial adhesion test and the weather resistance test respectively as follows:
First, initial adhesion test
the test method comprises the following steps: taking a 300 g ten thousand state sun sheet powder card, dividing the card into 70 pieces with the same area according to the size, dividing the card into 7 groups (10 pieces in each group), respectively and uniformly coating 6 adhesives in the embodiments on the first group to the sixth group, coating a common starch adhesive on the seventh group, then bonding the seventh group with paper (uncoated with the adhesive) with the same size, pressurizing for 10min, tearing the bonding part, and inspecting the bonding condition, wherein the initial adhesion test result is shown in the following table one:
Watch 1
in the above test, the non-napped portion is half-bonded, and the initial tack force is (M-M)/M100%, where M is the total area of the paper, M: the larger the initial tack, the stronger the tack of the adhesive.
The test results of table one above show that the initial tack of the adhesives of the 6 examples is 99%, while the initial tack of the conventional starch adhesive is only 90%, and the adhesive of the present invention is more adhesive than the conventional starch adhesive.
second, weather resistance test
the weather resistance of the invention refers to the capability of high temperature and high humidity resistance, low temperature resistance and high and low temperature cycle impact resistance, and the weather resistance test method comprises the following steps:
testing one: 120 pieces of paper are cut and taken, 30 pieces of paper are taken, the paper is divided into 6 groups (5 pieces in each group), the first group to the sixth group are respectively and correspondingly coated with 6 embodiments of adhesives which are respectively marked as samples Y1, Y2, Y3, Y4, Y5 and Y6, 30 pieces of paper are further taken and divided into 6 groups (5 pieces in each group), each group is coated with common starch adhesives which are marked as Y1 ', Y2', Y3 ', Y4', Y5 'and Y6', the samples coated with the adhesives are bonded with the other half of the paper, the paper is pressed for 2min, oven-dried at 80 ℃ for 30s, and a programmable constant temperature and humidity test box is used for weather resistance test.
and (2) testing: if no open-adhesive foaming phenomenon exists in the test, the viscosity of the adhesive after weather resistance is tested according to the initial adhesion test method.
The weather resistance test conditions, results and adhesion test results of the present invention are shown in the following table two:
Watch two
According to the test results of the second table, the viscosity of the modified adhesive is still 98% after weather resistance test, so that the modified adhesive disclosed by the invention can resist high and low temperatures of-25-70 ℃ and has the highest humidity of 96%, and after the weather resistance test of a common starch adhesive, the viscosity is reduced by 20% or the adhesive is directly opened and foamed, so that the large-scale industrial requirements cannot be met.
the above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention.
Claims (10)
1. the environment-friendly high-viscosity weather-resistant modified starch adhesive is characterized by comprising the following components in parts by weight:
2. the environment-friendly high-viscosity weather-resistant modified starch adhesive as claimed in claim 1, which is characterized by comprising the following components in parts by weight:
3. the environment-friendly, high-viscosity and weather-resistant modified starch adhesive as claimed in claim 1 or 2, wherein the carboxylic acid cross-linking agent is a dicarboxylic acid or a polycarboxylic acid.
4. The environmentally friendly, high viscosity, weatherable, modified starch adhesive of claim 3 wherein the dicarboxylic acid is food grade adipic acid.
5. The environment-friendly high-viscosity weather-resistant modified starch adhesive as claimed in claim 1 or 2, wherein the hydrogen peroxide is 29-32% by mass.
6. The environment-friendly high-viscosity weather-resistant modified starch adhesive as claimed in claim 1 or 2, wherein the polymerization degree of the polyvinyl alcohol is 1700-1800.
7. The environment-friendly high-viscosity weather-resistant modified starch adhesive as claimed in claim 1 or 2, wherein the auxiliary agent is at least one of a dispersing agent, a leveling wetting agent, a viscosity stabilizer and a defoaming agent:
The dispersing agent is potassium pyrophosphate, and the purity of the potassium pyrophosphate is analytically pure;
The leveling wetting agent is Dow Corning DC-67;
the viscosity stabilizer is butanol or phenol, and the purity of the butanol is analytically pure;
The antifoaming agent is Dow Corning DC-65 silicone antifoaming agent.
8. The environment-friendly, high-viscosity and weather-resistant modified starch adhesive as claimed in claim 1 or 2, wherein the soluble starch is at least one of rice starch, corn starch, millet starch, potato starch, sweet potato starch, wheat starch and pea starch, and the purity of the soluble starch is analytical grade.
9. The environment-friendly high-viscosity weather-resistant modified starch adhesive as claimed in claim 1 or 2, wherein the pH regulator is a sodium hydroxide solution with a mass fraction of 2%, the pasting agent is a sodium hydroxide solution with a mass fraction of 30%, and the pH regulator and the pasting agent are both prepared from sodium hydroxide with analytical purity and tertiary water.
10. the preparation method of the environment-friendly high-viscosity weather-resistant modified starch adhesive as claimed in claim 1 or 2, which is characterized by comprising the following steps:
s1, mixing: putting the three-necked bottle into a constant-temperature water bath kettle at 55-65 ℃, adding tertiary water into the three-necked bottle, adding polyvinyl alcohol when the temperature of the tertiary water is raised to 55-65 ℃, continuously stirring at the speed of 450-550 r/min, and adding soluble starch when the polyvinyl alcohol is completely dissolved to prepare a mixed solution;
s2, oxidation: adjusting the pH of the mixed solution to 9-10 by using a pH regulator, gradually adding hydrogen peroxide, adjusting the pH by using the pH regulator, keeping the pH of the mixed solution between 9 and 10, and continuously oxidizing for 2.5-3 hours;
s3, crosslinking: adding a carboxylic acid cross-linking agent, keeping the temperature at 55-65 ℃ and stirring for 0.5-1.5 hours;
s4, gelatinization: stopping heating, cooling the system to room temperature, and dropwise adding a gelatinizing agent one by one to gelatinize until the mixed solution becomes transparent;
S5, complexing: adding borax, and stirring for 15-45 minutes;
s6, dispersing: adding the auxiliary agent, stirring for 5-15 minutes, cooling, sealing and storing.
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