CN117887383A - Preparation method and application of plant fixing adhesive - Google Patents

Preparation method and application of plant fixing adhesive Download PDF

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Publication number
CN117887383A
CN117887383A CN202410303425.3A CN202410303425A CN117887383A CN 117887383 A CN117887383 A CN 117887383A CN 202410303425 A CN202410303425 A CN 202410303425A CN 117887383 A CN117887383 A CN 117887383A
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stirring
aqueous solution
reaction kettle
deionized water
controlling
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CN202410303425.3A
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CN117887383B (en
Inventor
杨志莹
张海良
吴府胜
张小羽
张云丽
孔祥彬
赵庆柱
刘新栋
马翠翠
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Weifang Academy Of Agricultural Sciences Weifang Branch Of Shandong Academy Of Agricultural Sciences
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Weifang Academy Of Agricultural Sciences Weifang Branch Of Shandong Academy Of Agricultural Sciences
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G2/00Vegetative propagation
    • A01G2/30Grafting
    • A01G2/38Holding; Ligating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Botany (AREA)
  • Developmental Biology & Embryology (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a preparation method and application of a plant fixing adhesive, belonging to the technical field of fixing adhesives, wherein the preparation method comprises the following steps: preparing modified kaolin, preparing branched particles, and mixing; adding corn starch, sodium hypochlorite aqueous solution and first deionized water into a reaction kettle, stirring, adding sodium hydroxide, continuously stirring, and pouring out to obtain modified starch solution; adding polyvinyl alcohol 1788 and a second part of deionized water into a reaction kettle, stirring, adding a potassium persulfate aqueous solution, stirring, adding a modified starch solution, stirring, adding a sodium sulfite aqueous solution, stirring, adding a citric acid aqueous solution, modified kaolin, branched particles and sodium alginate, and stirring to obtain a plant fixing adhesive; the plant fixing adhesive prepared by the invention can ensure air permeability, is impermeable, has high natural degradation speed, does not influence the normal growth of grafted buds, and does not need manual cleaning.

Description

Preparation method and application of plant fixing adhesive
Technical Field
The invention relates to the technical field of fixing adhesives, in particular to a preparation method and application of a plant fixing adhesive.
Background
The grafting bud grafting is a common grafting propagation method, the fixation of grafting buds is a key factor influencing the grafting survival rate, a mode of manually winding and fixing a plastic film is generally adopted in production, but the mode is long in time consumption, and the problems of loose film breakage and the like easily occur in the operation process, so that grafting failure is caused, and the production efficiency is influenced.
In order to improve grafting efficiency, the most commonly used method at present is to use plant fixing glue to replace a plastic film, and specifically to use plant fixing glue to fix grafting buds on a stock rapidly, wherein the plant fixing glue needs to be waterproof while guaranteeing ventilation, and is fast in natural degradation speed, so that the plant fixing glue needs to be guaranteed not to influence the respiration of grafting buds, the grafting buds can be protected from being contacted with water, the grafting buds are prevented from being rotten after being contacted with water, the grafting buds need to be naturally degraded, healing of the grafting buds is achieved, manual removal is not needed after germination, and workload is reduced. The plant fixing glue commonly used at present is polyvinyl alcohol glue and acrylic ester glue, but the use effect on plant grafting is affected due to the defects of poor air permeability, strong water permeability and slow natural degradation speed when the plant fixing glue is used.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the plant fixing adhesive and the preparation method thereof, and the prepared plant fixing adhesive can be waterproof while ensuring ventilation, has high natural degradation speed, does not influence the normal growth of grafting buds, and does not need manual cleaning.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the plant fixing glue comprises the following steps: preparing modified kaolin, preparing branched particles, and mixing;
the preparation of the modified kaolin comprises the following steps: primary modification and secondary modification;
the first-stage modification, mixing nano kaolin, zinc nitrate aqueous solution, polyvinylpyrrolidone, absolute ethyl alcohol and deionized water, performing ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 20-30kHz, controlling the time to be 50-60min, adding the mixture into a reaction kettle after the ultrasonic oscillation is finished, controlling the temperature of the reaction kettle to be 30-50 ℃, controlling the stirring speed to be 100-300rpm, dropwise adding sodium hydroxide aqueous solution to adjust the pH value to 9-9.5, then dropwise adding tetraethoxysilane into the reaction kettle, continuing stirring for 20-30min after the dropwise adding, adding alkyl glycoside APG-0810 and dodecyl betaine, continuing stirring for 7-8h, filtering, cleaning filter residues by using deionized water for 3-4 times, drying at 80-90 ℃, and roasting at 350-450 ℃ for 3-4h to obtain first-stage modified kaolin;
In the primary modification, the mass ratio of nano kaolin to zinc nitrate aqueous solution to polyvinylpyrrolidone to absolute ethyl alcohol to deionized water to tetraethoxysilane to alkyl glycoside APG-0810 to dodecyl betaine is 20-25:10-12:10-12:200-230:300-350:32-35:5-7:4-5;
The concentration of the zinc nitrate aqueous solution is 2wt%;
The concentration of the sodium hydroxide aqueous solution is 10wt%;
the dropping speed of the sodium hydroxide aqueous solution is 1-2g/min;
the dripping speed of the tetraethoxysilane is 3-3.5g/min;
The particle size of the nano kaolin is 200-300nm;
Adding the first-stage modified kaolin, deionized water, methyltrimethoxysilane and 3-aminopropyl trimethoxysilane into a reaction kettle, controlling the temperature of the reaction kettle to 40-60 ℃, controlling the stirring speed to 400-500rpm, stirring for 20-40min, adding sodium hydroxide aqueous solution to adjust the pH to 8.5-9.5, continuously stirring for 20-22h, freeze-drying at-50-40 ℃ for 30-35h, and grinding to the particle size of 4-5 mu m to obtain modified kaolin;
In the secondary modification, the mass ratio of the primary modified kaolin to the deionized water to the methyltrimethoxysilane to the 3-aminopropyl trimethoxysilane is 100-110:130-150:20-30:2-3;
The concentration of the sodium hydroxide aqueous solution is 10wt%;
the preparation of branched particles consists of the following steps: carboxylation, branching;
Adding a silane coupling agent KH550, succinic anhydride and a first part of N, N-dimethylformamide into a reaction kettle, controlling the temperature of the reaction kettle to 60-70 ℃, controlling the stirring speed to 100-200rpm, stirring for 2-3h, adding nano silicon dioxide, a second part of N, N-dimethylformamide and deionized water, controlling the stirring speed to 400-500rpm, continuing stirring for 6-7h, filtering, cleaning filter residues with deionized water for 3-4 times, and drying at 80-90 ℃ to obtain carboxylated silicon dioxide;
In the carboxylation, the mass ratio of the silane coupling agent KH550 to the succinic anhydride to the first part of N, N-dimethylformamide to the nano silicon dioxide to the second part of N, N-dimethylformamide to the deionized water is 1.4-1.6:0.7-0.8:30-35:20-23:250-300:7-9;
the particle size of the nano silicon dioxide is 100nm;
Adding branched polyethyleneimine, carboxylated silicon dioxide and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 30-35 ℃, controlling the stirring speed to be 100-300rpm, stirring for 3-4 hours, filtering, cleaning filter residues with deionized water for 3-4 times, and drying at 80-90 ℃ to obtain branched particles;
In the branching, the mass ratio of branched polyethyleneimine to carboxylated silicon dioxide to deionized water is 6-7:30-35:100-120;
The weight average molecular weight of the branched polyethyleneimine is 20000-30000;
Adding corn starch, sodium hypochlorite aqueous solution and first deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, controlling the stirring speed to be 100-300rpm, stirring for 40-60min, adding sodium hydroxide, continuously stirring for 70-90min, and pouring out to obtain modified starch solution; adding polyvinyl alcohol 1788 and a second part of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 50-60 ℃, controlling the stirring speed to 100-300rpm, stirring for 20-30min, adding a potassium persulfate aqueous solution, stirring for 30-50min, adding a modified starch solution, stirring for 40-60min, adding a sodium sulfite aqueous solution, stirring for 20-40min, adding a citric acid aqueous solution, modified kaolin, branched particles and sodium alginate, controlling the temperature of the reaction kettle to 75-85 ℃, stirring for 40-60min, pouring out, and filling into a packaging bottle to obtain the plant fixing glue;
In the course of the mixing, the mixture, the mass ratio of corn starch, sodium hypochlorite aqueous solution, first part of deionized water, sodium hydroxide, polyvinyl alcohol 1788, second part of deionized water, potassium persulfate aqueous solution, sodium sulfite aqueous solution, citric acid aqueous solution, modified kaolin, branched particles and sodium alginate is 100-110:20-25:280-300:2-3:150-180:350-380:8-10:20-25:150-170:30-35:8-10:4-5;
The concentration of the sodium hypochlorite aqueous solution is 30wt%;
the concentration of the potassium persulfate aqueous solution is 4wt%;
the concentration of the sodium sulfite aqueous solution is 20wt%;
The concentration of the aqueous solution of citric acid is 10wt%;
The plant fixing adhesive prepared by the preparation method is applied, in spring or autumn, grafting buds needing to be subjected to bud grafting are aligned with cambium of the stock, the plant fixing adhesive is smeared around bud eyes of the grafting buds, the plant fixing adhesive can be smeared on all parts, except the bud eyes, of the grafting buds, which are contacted with the stock, when the plant fixing adhesive is smeared, the grafting buds are healed, the fixing adhesive can be naturally degraded after the grafting buds germinate, and manual cleaning is not needed.
Compared with the prior art, the invention has the beneficial effects that:
(1) The curing time of the plant fixing glue prepared by the invention is 6.9-7.2s, and the bonding strength is 5.87-6.20MPa;
(2) The preparation method of the plant fixing adhesive can ensure ventilation and water impermeability, the plant fixing adhesive prepared by the invention is smeared on a polytetrafluoroethylene plate, the smearing thickness is controlled to be 2mm, after curing for 1d at 25 ℃, the adhesive film is torn off, the ventilation index of the adhesive film is 2350-2470g/m 2/24 h, the adhesive film is completely soaked in deionized water, and the mass change rate after being completely soaked for 24h at 25 ℃ is 0.1-0.2%;
(3) The preparation method of the plant fixing glue can improve the natural degradation speed of the plant fixing glue, and the mass change rate of the plant fixing glue prepared by the preparation method is 84.1-85.5% after the plant fixing glue is solidified and placed in an environment with the temperature of 25 ℃ and the humidity of 50% for 100 d.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A preparation method of a plant fixing adhesive specifically comprises the following steps:
1. Preparation of modified kaolin:
(1) First-stage modification: mixing 20g of nano kaolin, 10g of zinc nitrate aqueous solution with the concentration of 2wt%, 10g of polyvinylpyrrolidone, 200g of absolute ethyl alcohol and 300g of deionized water, performing ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 20kHz, the time to be 50min, adding the mixture into a reaction kettle after the ultrasonic oscillation is finished, controlling the temperature of the reaction kettle to be 30 ℃, controlling the stirring speed to be 100rpm, dropwise adding sodium hydroxide aqueous solution with the concentration of 10wt% to adjust the pH value to 9 at the dropwise adding speed of 1g/min, then dropwise adding 32g of ethyl orthosilicate into the reaction kettle, controlling the dropwise adding speed to be 3g/min, continuing stirring for 20min after the dropwise adding, adding 5g of alkyl glycoside APG-0810 and 4g of dodecyl betaine, continuing stirring for 7h, filtering, cleaning filter residues by using deionized water for 3 times, drying at 80 ℃, and roasting at 350 ℃ for 3h to obtain the first-stage modified kaolin;
The particle size of the nano kaolin is 200nm;
(2) And (3) secondary modification: adding 100g of primary modified kaolin, 130g of deionized water, 20g of methyltrimethoxysilane and 2g of 3-aminopropyl trimethoxysilane into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 400rpm, stirring for 20min, adding 10wt% concentration sodium hydroxide aqueous solution to adjust the pH to 8.5, continuing stirring for 20h, freeze-drying for 30h at-50 ℃, and grinding to the particle size of 4 mu m to obtain modified kaolin;
2. preparing branched particles:
(1) Carboxylation: adding 1.4g of silane coupling agent KH550, 0.7g of succinic anhydride and 30g of N, N-dimethylformamide into a reaction kettle, controlling the temperature of the reaction kettle to 60 ℃, controlling the stirring speed to 100rpm, stirring for 2 hours, adding 20g of nano silicon dioxide, 250g of N, N-dimethylformamide and 7g of deionized water, controlling the stirring speed to 400rpm, continuing stirring for 6 hours, filtering, cleaning filter residues with deionized water for 3 times, and drying at 80 ℃ to obtain carboxylated silicon dioxide;
the particle size of the nano silicon dioxide is 100nm;
(2) Branching: adding 6g of branched polyethylenimine, 30g of carboxylated silicon dioxide and 100g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, controlling the stirring speed to 100rpm, stirring for 3 hours, filtering, cleaning filter residues with deionized water for 3 times, and drying at 80 ℃ to obtain branched particles;
The weight average molecular weight of the branched polyethyleneimine is 20000;
3. Mixing: adding 100g of corn starch, 20g of 30wt% sodium hypochlorite aqueous solution and 280g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 60 ℃, controlling the stirring speed to 100rpm, stirring for 40min, adding 2g of sodium hydroxide, continuously stirring for 70min, and pouring out to obtain modified starch solution; adding 150g of polyvinyl alcohol 1788 and 350g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 100rpm, stirring for 20min, adding 8g of potassium persulfate aqueous solution with the concentration of 4wt%, stirring for 30min, adding modified starch solution, stirring for 40min, adding 20g of sodium sulfite aqueous solution with the concentration of 20wt%, stirring for 20min, adding 150g of citric acid aqueous solution with the concentration of 10wt%, 30g of modified kaolin, 8g of branched particles and 4g of sodium alginate, controlling the temperature of the reaction kettle to 75 ℃, stirring for 40min, pouring out, and filling into a packaging bottle to obtain the plant fixing glue.
The embodiment also provides an application of the plant fixing glue, which specifically comprises the following steps: in spring, avoiding rainy season and extreme weather, aligning grafting buds to be subjected to bud grafting with cambium of the stock, smearing plant fixing glue around bud eyes of the grafting buds, ensuring that the plant fixing glue can be smeared on all parts, except the bud eyes, of the grafting buds, which are contacted with the stock, and the fixing glue can be naturally degraded after the grafting buds heal and germinate without manual cleaning.
Example 2
A preparation method of a plant fixing adhesive specifically comprises the following steps:
1. Preparation of modified kaolin:
(1) First-stage modification: mixing 22g of nano kaolin, 11g of zinc nitrate aqueous solution with the concentration of 2wt%, 11g of polyvinylpyrrolidone, 220g of absolute ethyl alcohol and 320g of deionized water, carrying out ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 25kHz, the time to be 55min, adding the mixture into a reaction kettle after the ultrasonic oscillation is finished, controlling the temperature of the reaction kettle to be 40 ℃, controlling the stirring speed to be 200rpm, dropwise adding 10wt% sodium hydroxide aqueous solution with the concentration of 1.5g/min to adjust the pH value to 9.2, then dropwise adding 34g of tetraethoxysilane into the reaction kettle, controlling the dropwise adding speed to be 3.2g/min, continuing stirring for 25min after the dropwise adding, adding 6g of alkyl glycoside APG-0810 and 4.5g of dodecyl betaine, continuing stirring for 7.5h, filtering, washing filter residues with deionized water for 3 times, drying at 85 ℃, and roasting at 400 ℃ for 3.5h to obtain the first-stage modified kaolin;
The particle size of the nano kaolin is 200nm;
(2) And (3) secondary modification: adding 105g of primary modified kaolin, 140g of deionized water, 25g of methyltrimethoxysilane and 2.5g of 3-aminopropyl trimethoxysilane into a reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 450rpm, stirring for 30min, adding 10wt% concentration sodium hydroxide aqueous solution to adjust the pH to 9, continuing stirring for 21h, freeze-drying at-45 ℃ for 32h, and grinding to the particle size of 4 mu m to obtain modified kaolin;
2. preparing branched particles:
(1) Carboxylation: adding 1.5g of a silane coupling agent KH550, 0.7g of succinic anhydride and 32g of N, N-dimethylformamide into a reaction kettle, controlling the temperature of the reaction kettle to 65 ℃, controlling the stirring speed to 200rpm, stirring for 2.5h, adding 22g of nano silicon dioxide, 280g of N, N-dimethylformamide and 8g of deionized water, controlling the stirring speed to 500rpm, continuing stirring for 6.5h, filtering, washing filter residues with deionized water for 4 times, and drying at 85 ℃ to obtain carboxylated silicon dioxide;
the particle size of the nano silicon dioxide is 100nm;
(2) Branching: adding 6.5g of branched polyethylenimine, 32g of carboxylated silicon dioxide and 110g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 32 ℃, controlling the stirring speed to 200rpm, stirring for 3.5h, filtering, cleaning filter residues with deionized water for 4 times, and drying at 85 ℃ to obtain branched particles;
the branched polyethyleneimine has a weight average molecular weight of 30000;
3. Mixing: adding 105g of corn starch, 22g of 30wt% sodium hypochlorite aqueous solution and 290g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 65 ℃, controlling the stirring speed to 200rpm, stirring for 50min, adding 2.5g of sodium hydroxide, continuously stirring for 80min, and pouring out to obtain modified starch solution; adding 160g of polyvinyl alcohol 1788 and 370g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 55 ℃, controlling the stirring speed to 200rpm, stirring for 25min, adding 9g of 4wt% potassium persulfate aqueous solution, stirring for 40min, adding modified starch solution, stirring for 50min, adding 22g of 20wt% sodium sulfite aqueous solution, stirring for 30min, adding 160g of 10wt% citric acid aqueous solution, 32g of modified kaolin, 9g of branched particles and 4.5g of sodium alginate, controlling the temperature of the reaction kettle to 80 ℃, stirring for 50min, pouring out, and filling into a packaging bottle to obtain the plant fixing glue.
The embodiment also provides an application of the plant fixing glue, which specifically comprises the following steps: in autumn, avoiding rainy season and extreme weather, aligning grafting buds to be subjected to bud grafting with cambium of the stock, smearing plant fixing glue around bud eyes of the grafting buds, ensuring that the plant fixing glue can be smeared on all parts, except the bud eyes, of the grafting buds, which are contacted with the stock, and the fixing glue can be naturally degraded after the grafting buds heal and germinate without manual cleaning.
Example 3
A preparation method of a plant fixing adhesive specifically comprises the following steps:
1. Preparation of modified kaolin:
(1) First-stage modification: mixing 25g of nano kaolin, 12g of zinc nitrate aqueous solution with the concentration of 2wt%, 12g of polyvinylpyrrolidone, 230g of absolute ethyl alcohol and 350g of deionized water, carrying out ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 30kHz, the time to be 60min, adding the mixture into a reaction kettle after the ultrasonic oscillation is finished, controlling the temperature of the reaction kettle to be 50 ℃, controlling the stirring speed to be 300rpm, dropwise adding 10wt% sodium hydroxide aqueous solution with the dropwise adding speed of 2g/min to adjust the pH value to 9.5, then dropwise adding 35g of ethyl orthosilicate into the reaction kettle, controlling the dropwise adding speed to be 3.5g/min, continuing stirring for 30min after the dropwise adding, adding 7g of alkyl glycoside APG-0810 and 5g of dodecyl betaine, continuing stirring for 8h, filtering, washing filter residues with deionized water for 4 times, drying at 90 ℃, and roasting at 450 ℃ for 4h to obtain first-stage modified kaolin;
The particle size of the nano kaolin is 300nm;
(2) And (3) secondary modification: adding 110g of primary modified kaolin, 150g of deionized water, 30g of methyltrimethoxysilane and 3g of 3-aminopropyl trimethoxysilane into a reaction kettle, controlling the temperature of the reaction kettle to 60 ℃, controlling the stirring speed to 500rpm, stirring for 40min, adding 10wt% concentration sodium hydroxide aqueous solution to adjust the pH to 9.5, continuing stirring for 22h, freeze-drying at-40 ℃ for 35h, and grinding to the particle size of 5 mu m to obtain modified kaolin;
2. preparing branched particles:
(1) Carboxylation: adding 1.6g of silane coupling agent KH550, 0.8g of succinic anhydride and 35g of N, N-dimethylformamide into a reaction kettle, controlling the temperature of the reaction kettle to 70 ℃, controlling the stirring speed to 200rpm, stirring for 3 hours, adding 23g of nano silicon dioxide, 300g of N, N-dimethylformamide and 9g of deionized water, controlling the stirring speed to 500rpm, continuing stirring for 7 hours, filtering, cleaning filter residues by using deionized water for 4 times, and drying at 90 ℃ to obtain carboxylated silicon dioxide;
the particle size of the nano silicon dioxide is 100nm;
(2) Branching: adding 7g of branched polyethylenimine, 35g of carboxylated silicon dioxide and 120g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 35 ℃, controlling the stirring speed to 300rpm, stirring for 4 hours, filtering, cleaning filter residues with deionized water for 4 times, and drying at 90 ℃ to obtain branched particles;
the branched polyethyleneimine has a weight average molecular weight of 30000;
3. Mixing: adding 110g of corn starch, 25g of 30wt% sodium hypochlorite aqueous solution and 300g of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 70 ℃, controlling the stirring speed to 300rpm, stirring for 60min, adding 3g of sodium hydroxide, continuously stirring for 90min, and pouring out to obtain modified starch solution; 180g of polyvinyl alcohol 1788 and 380g of deionized water are added into a reaction kettle, the temperature of the reaction kettle is controlled to 60 ℃, the stirring speed is controlled to 300rpm, stirring is carried out for 30min, 10g of potassium persulfate aqueous solution with the concentration of 4wt% is added, stirring is carried out for 50min, modified starch solution is added, stirring is carried out for 60min, 25g of sodium sulfite aqueous solution with the concentration of 20wt% is added, stirring is carried out for 40min, 170g of citric acid aqueous solution with the concentration of 10wt%, 35g of modified kaolin, 10g of branched particles and 5g of sodium alginate are added, the temperature of the reaction kettle is controlled to 85 ℃, stirring is carried out for 60min, and pouring and packaging are carried out in a packaging bottle, thus obtaining the plant fixing glue.
The embodiment also provides an application of the plant fixing glue, which specifically comprises the following steps: in spring, avoiding rainy season and extreme weather, aligning grafting buds to be subjected to bud grafting with cambium of the stock, smearing plant fixing glue around bud eyes of the grafting buds, ensuring that the plant fixing glue can be smeared on all parts, except the bud eyes, of the grafting buds, which are contacted with the stock, and the fixing glue can be naturally degraded after the grafting buds heal and germinate without manual cleaning.
Comparative example 1
In order to verify the effect of primary modification in the modified kaolin, the preparation method of the plant fixing glue in the embodiment 2 is adjusted, specifically, the step (1) of primary modification in the step (1) of preparing the modified kaolin is omitted, and the nano kaolin with the particle size of 200nm is replaced by the same amount of the primary modified kaolin in the step (2) of secondary modification.
Comparative example 2
To verify the effect of the branched particles, the preparation method of the fixing glue for plants of example 2 was modified, specifically omitting the step of preparing the branched particles in step 2 and omitting the addition of the branched particles in the step of mixing in step 3.
Test example 1
The curing speed and the adhesive strength of the fixing adhesives for plants prepared in examples 1 to 3 and comparative examples 1 to 2 were tested, and the air permeability index of the fixing adhesives for plants after curing was tested, and the test results were as follows:
the curing time test method comprises the following steps: 10g of plant is smeared on a smooth and flat glass surface by using a fixing adhesive, and then is placed in an environment with the temperature of 25 ℃ for solidification, and the time from smearing to no longer sticking hands is recorded.
The method for testing the air permeability index comprises the following steps: the plant fixing adhesive prepared in examples 1 to 3 and comparative examples 1 to 2 was applied to a polytetrafluoroethylene plate, the thickness of the applied film was controlled to be 2mm, the adhesive film was peeled off after curing at 25℃for 1d, cut into a size of 3cm X3 cm, and then fixed to a permeability tester, the pressure difference was adjusted to 1kPa, and then the permeated air flow was tested, and the test was repeated 3 times for each adhesive film, and the average value was calculated, and the air permeability index was obtained by dividing the average value by the contact area with air.
From the above results, it can be seen that the air permeability of the prepared plant fixing glue can be improved by performing the first-order modification in the preparation of the modified kaolin; branched particles are added in the preparation of the plant fixing glue, so that the curing speed, the bonding strength and the air permeability of the prepared plant fixing glue can be improved;
The preparation of the modified kaolin is divided into two steps, namely primary modification and secondary modification, wherein the primary modification is to coat the nano kaolin by zinc ions and silicon dioxide, the secondary modification is to graft the silicon dioxide in the primary modification by methyltrimethoxysilane and 3-aminopropyl trimethoxysilane, wherein the zinc ions and the silicon dioxide are used for improving the antibacterial property, natural degradation speed and air permeability of the nano kaolin, the zinc ions have antibacterial property, the influence of bacteria on the healing and germination of grafting buds can be avoided, the silicon dioxide has a loose porous structure, the porosity of the fixing glue can be improved, the air permeability of the fixing glue is improved, and the silicon dioxide also has the effect of promoting the degradation of the fixing glue; the purpose of grafting by using methyltrimethoxysilane is to improve the hydrophobicity of the nano kaolin, ensure that moisture cannot enter the nano kaolin and the inside of silicon dioxide, and the purpose of modifying by using 3-aminopropyl trimethoxysilane is to perform amino functionalization on the surface of the silicon dioxide;
The branched particles are a compound of branched polyethyleneimine and carboxylated silica, amino groups on the branched polyethyleneimine react with carboxyl groups on the surface of the carboxylated silica, so that the branched polyethyleneimine and the carboxylated silica are compounded, hydrophobic cross-linked amide bonds are formed on the surface of the compounded carboxylated silica, and multiple cross-links can be formed between the branched polyethyleneimine and modified starch solution, polyvinyl alcohol solution and sodium alginate during curing, so that quick curing is realized, the bonding strength is improved, and the air permeability can be further improved due to the porous structure of the carboxylated silica after surface cross-linking.
Test example 2
The water permeability of the plant fixing adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 was tested, specifically:
The plant fixing adhesives prepared in examples 1-3 and comparative examples 1-2 were respectively coated on a polytetrafluoroethylene plate, the coating thickness was controlled to be 2mm, after curing for 1d at 25 ℃, the adhesive films were peeled off, fixing adhesive samples with the mass of 100g were respectively cut off, then the fixing adhesive samples were respectively and completely soaked in deionized water, at 25 ℃ for 24 hours, the moisture on the surfaces was wiped off after taking out, weighing was performed, and the mass change rate before and after soaking was calculated, and the calculation results were as follows:
From the above results, it can be seen that the first-order modification in the preparation of the modified kaolin and the addition of branched particles in the preparation of the plant fixing glue can both improve the hydrophobicity of the prepared plant fixing glue;
The surface of the kaolin subjected to the first-stage modification has more hydroxyl groups, and can be combined with methyl trimethoxy silane and 3-aminopropyl trimethoxy silane, so that the hydrophobicity of the fixing adhesive is improved; the branched particles can introduce amide groups, i.e. more hydrophobic groups, thereby increasing the hydrophobicity of the fixing glue.
Test example 3
The natural degradation rate of the plant fixing adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 was tested, specifically:
After the plant fixing adhesives prepared in examples 1-3 and comparative examples 1-2 were completely cured, 200g of each fixing adhesive sample was placed in an environment with a temperature of 25 ℃ and a humidity of 50% and left to stand for 100d for weighing, and the fixing adhesives were used as mass after natural degradation, and the mass change rates before and after natural degradation were calculated according to the following calculation formulas and calculation results:
Mass change rate= (200-mass after natural degradation)/200×100%;
from the above results, it can be seen that the natural degradation rate of the prepared plant fixing glue can be improved by performing the first-order modification in the preparation of the modified kaolin and adding the branched particles in the preparation of the plant fixing glue;
The silicon dioxide coating layer introduced in the primary modification and the carboxylated silicon dioxide introduced in the branched particles can all improve the natural degradation speed of the fixing glue.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The preparation method of the plant fixing glue is characterized by comprising the following steps of: preparing modified kaolin, preparing branched particles, and mixing;
the preparation of the modified kaolin comprises the following steps: primary modification and secondary modification;
The first-stage modification, mixing nano kaolin, zinc nitrate aqueous solution, polyvinylpyrrolidone, absolute ethyl alcohol and deionized water, performing ultrasonic oscillation, adding the mixture into a reaction kettle after the ultrasonic oscillation is finished, controlling the temperature of the reaction kettle to be 30-50 ℃, starting stirring, dropwise adding sodium hydroxide aqueous solution to adjust the pH value to 9-9.5, then dropwise adding tetraethoxysilane into the reaction kettle, continuing stirring after the dropwise adding is finished, adding alkyl glycoside APG-0810 and dodecyl betaine, continuing stirring, filtering, cleaning, drying filter residues, and roasting at 350-450 ℃ to obtain the first-stage modified kaolin;
adding the first-stage modified kaolin, deionized water, methyltrimethoxysilane and 3-aminopropyl trimethoxysilane into a reaction kettle, controlling the temperature of the reaction kettle to 40-60 ℃, stirring, adding a sodium hydroxide aqueous solution to adjust the pH to 8.5-9.5, continuing stirring, freeze-drying and grinding to obtain modified kaolin;
the preparation of branched particles consists of the following steps: carboxylation, branching;
Adding a silane coupling agent KH550, succinic anhydride and a first part of N, N-dimethylformamide into a reaction kettle, controlling the temperature of the reaction kettle to 60-70 ℃, stirring, adding nano silicon dioxide, a second part of N, N-dimethylformamide and deionized water, continuously stirring, filtering, cleaning and drying filter residues to obtain carboxylated silicon dioxide;
Adding branched polyethylenimine, carboxylated silicon dioxide and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 30-35 ℃, stirring, filtering, cleaning and drying filter residues to obtain branched particles;
Adding corn starch, sodium hypochlorite aqueous solution and first deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 60-70 ℃, stirring, adding sodium hydroxide, continuously stirring, and pouring out to obtain modified starch solution; adding polyvinyl alcohol 1788 and a second part of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 50-60 ℃, stirring, adding a potassium persulfate aqueous solution, stirring, adding a modified starch solution, stirring, adding a sodium sulfite aqueous solution, stirring, adding a citric acid aqueous solution, modified kaolin, branched particles and sodium alginate, controlling the temperature of the reaction kettle to 75-85 ℃, and stirring to obtain the plant fixing glue.
2. The method for preparing plant fixing glue according to claim 1, wherein in the first-order modification, the mass ratio of nano kaolin, zinc nitrate aqueous solution, polyvinylpyrrolidone, absolute ethyl alcohol, deionized water, tetraethoxysilane, alkyl glycoside APG-0810, dodecyl betaine is 20-25:10-12:10-12:200-230:300-350:32-35:5-7:4-5;
The concentration of the zinc nitrate aqueous solution is 2wt%;
The concentration of the sodium hydroxide aqueous solution is 10wt%;
the dropping speed of the sodium hydroxide aqueous solution is 1-2g/min;
the dripping speed of the tetraethoxysilane is 3-3.5g/min;
the particle size of the nano kaolin is 200-300nm.
3. The method for preparing a plant fixing glue according to claim 1, wherein in the secondary modification, the mass ratio of the first-order modified kaolin, deionized water, methyltrimethoxysilane and 3-aminopropyl trimethoxysilane is 100-110:130-150:20-30:2-3;
the concentration of the aqueous sodium hydroxide solution was 10wt%.
4. The preparation method of the plant fixing glue according to claim 1, wherein in the carboxylation, the mass ratio of the silane coupling agent KH550, succinic anhydride, the first part of N, N-dimethylformamide, nano-silica, the second part of N, N-dimethylformamide and deionized water is 1.4-1.6:0.7-0.8:30-35:20-23:250-300:7-9;
The particle size of the nano silicon dioxide is 100nm.
5. The method for preparing a plant fixing glue according to claim 1, wherein in the branching, the mass ratio of branched polyethyleneimine, carboxylated silica, deionized water is 6-7:30-35:100-120;
The weight average molecular weight of the branched polyethyleneimine is 20000-30000.
6. The method for preparing a plant fixing glue according to claim 1, wherein in the mixing, the mass ratio of corn starch, sodium hypochlorite aqueous solution, first part of deionized water, sodium hydroxide, polyvinyl alcohol 1788, second part of deionized water, potassium persulfate aqueous solution, sodium sulfite aqueous solution, citric acid aqueous solution, modified kaolin, branched particles, sodium alginate is 100-110:20-25:280-300:2-3:150-180:350-380:8-10:20-25:150-170:30-35:8-10:4-5;
The concentration of the sodium hypochlorite aqueous solution is 30wt%;
the concentration of the potassium persulfate aqueous solution is 4wt%;
the concentration of the sodium sulfite aqueous solution is 20wt%;
the concentration of the aqueous solution of citric acid is 10wt%.
7. The use of a plant fixative prepared by the preparation method of any one of claims 1 to 6, characterized in that grafting buds to be subjected to bud grafting are aligned with cambium of a stock in spring or autumn, avoiding rainy season and extreme weather, the plant fixative is smeared around bud eyes of the grafting buds, the plant fixative is smeared on all parts of the grafting buds except the bud eyes, which are contacted with the stock, after the grafting buds heal, the fixative can be naturally degraded without manual cleaning after germination.
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