CN112011292B - Water-based high-speed nozzle connecting adhesive and preparation method thereof - Google Patents

Water-based high-speed nozzle connecting adhesive and preparation method thereof Download PDF

Info

Publication number
CN112011292B
CN112011292B CN202010866413.3A CN202010866413A CN112011292B CN 112011292 B CN112011292 B CN 112011292B CN 202010866413 A CN202010866413 A CN 202010866413A CN 112011292 B CN112011292 B CN 112011292B
Authority
CN
China
Prior art keywords
viscosity
emulsion
water
vae emulsion
polyvinyl alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010866413.3A
Other languages
Chinese (zh)
Other versions
CN112011292A (en
Inventor
高金宪
高帅
岳喜英
费玉坤
刘龙江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou Shenhuo Glue Co ltd
Original Assignee
Zhengzhou Shenhuo Glue Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou Shenhuo Glue Co ltd filed Critical Zhengzhou Shenhuo Glue Co ltd
Priority to CN202010866413.3A priority Critical patent/CN112011292B/en
Publication of CN112011292A publication Critical patent/CN112011292A/en
Application granted granted Critical
Publication of CN112011292B publication Critical patent/CN112011292B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09J131/00—Adhesives 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The application relates to the technical field of cigarette glue, and particularly discloses water-based high-speed nozzle glue and a preparation method thereof. The water-based high-speed nozzle adhesive is mainly prepared from water and the following raw materials in parts by weight: 83-86 parts of VAE emulsion, 8-11 parts of polyvinyl alcohol solution, 0.1-0.2 part of bactericide and 0.1-0.2 part of defoaming agent; the VAE emulsion consists of high-viscosity VAE emulsion, medium-viscosity VAE emulsion and low-viscosity VAE emulsion according to the weight ratio of 10-15:30-40: 30-40; the viscosity of the high-viscosity VAE emulsion is 2500-3700mpa & s; the viscosity of the medium-viscosity VAE emulsion is 1500-2500mpa & s; the viscosity of the low-viscosity VAE emulsion is 180-2200 mpa-s. The water-based high-speed nozzle adhesive has high fluidity and is more suitable for a high-speed spraying process.

Description

Water-based high-speed nozzle connecting adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of cigarette glue, in particular to water-based high-speed mouth connecting glue and a preparation method thereof.
Background
The cigarette comprises main components such as tobacco shreds, tobacco essence and the like, and also comprises important auxiliary materials such as a bonding filter stick, cigarette paper, tipping paper, a packaging box and the like, wherein the auxiliary materials are required to be bonded, and the cigarette adhesive used in bonding has great influence on the quality of the cigarette. The cigarette adhesive comprises a mouth-connecting adhesive, a filter stick adhesive, a middle seam adhesive, a decal adhesive, a small box sealing adhesive, a large box packaging adhesive and the like, wherein the mouth-connecting adhesive is a cigarette adhesive with a very large use amount.
The nozzle glue is required to be non-toxic, odorless and pollution-free, has proper viscosity and good stability, and also has the performances of high bonding speed, uniform spraying, smooth bonding and the like. Therefore, the nozzle rubber should have a suitable viscosity and a suitable fluidity. At present, many nozzle adhesives are developed on the basis of polyvinyl acetate emulsion, and with the development of nozzle adhesive technology, the usage amount of vinyl acetate-ethylene copolymer emulsion (VAE) is larger and larger.
However, the VAE emulsion adhesive film has poor water resistance, and less ideal solvent resistance and acid and alkali resistance, and most of the prior nozzle adhesives take VAE as a substrate and are further modified to obtain the nozzle adhesive with excellent performance.
The application publication number of CN106928885A of the invention is Chinese patent application, which discloses a high flame-retardant cigarette filter tip adhesive, which is composed of the following raw materials in parts by mass: 850 parts of vinyl acetate-ethylene copolymer, 80-120 parts of 15% polyvinyl alcohol aqueous solution, 3-5 parts of surfactant, 10-20 parts of flame retardant, 0.5-1.0 part of defoaming agent, 0.5-1.0 part of sodium hydroxide and 50-100 parts of deionized water. The nozzle glue has good flame retardance and higher safety, but the fluidity of the nozzle glue still needs to be improved, the dilution stability is poorer, the nozzle glue is not suitable for high-speed spraying, and the production efficiency of cigarettes is influenced
Disclosure of Invention
In order to improve the fluidity and dilution stability of the nozzle glue, the application provides the water-based high-speed nozzle glue and the preparation method thereof.
In a first aspect, the application provides a water-based high-speed nozzle adhesive which adopts the following technical scheme:
a water-based high-speed nozzle connecting adhesive is mainly prepared from water and the following raw materials in parts by weight: 83-86 parts of VAE emulsion, 8-11 parts of polyvinyl alcohol solution, 0.1-0.2 part of bactericide and 0.1-0.2 part of defoaming agent; the VAE emulsion consists of high-viscosity VAE emulsion, medium-viscosity VAE emulsion and low-viscosity VAE emulsion according to the weight ratio of 10-15:30-40: 30-40; the viscosity of the high-viscosity VAE emulsion is 2500-3700mpa & s; the viscosity of the medium-viscosity VAE emulsion is 1500-2500mpa & s; the viscosity of the low-viscosity VAE emulsion is 180-2200 mpa-s.
By adopting the technical scheme, the VAE emulsion adopts three emulsions of high-viscosity VAE emulsion, medium-viscosity VAE emulsion and low-viscosity VAE emulsion with sequentially reduced viscosity to form VAE mixed emulsion, the vinyl acetate-ethylene copolymers in the three emulsions have different polymerization degrees and different crosslinking degrees, and are easy to disperse uniformly during mixing, so that the flowability and dilution stability of the VAE emulsion can be greatly improved, and the high-speed spraying is facilitated. After the three VAE emulsions with different viscosities are combined according to the proportion, a mixed emulsion with proper and stable viscosity can be obtained, the mechanical stability and the environmental stability of the finally prepared nozzle adhesive are improved, and the storage and the spraying are facilitated. After the polyvinyl alcohol is added, the polyvinyl alcohol can be grafted with a long chain of a vinyl acetate-ethylene copolymer in the VAE emulsion to generate a cross-linking substance with a complex structure, so that the strength and toughness of a bonding film layer when the nozzle adhesive is used are improved, and the stability of the nozzle adhesive is also improved.
Preferably, the water-based high-speed nozzle adhesive is mainly prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide and 0.1 part of defoaming agent; the VAE emulsion consists of high-viscosity VAE emulsion, medium-viscosity VAE emulsion and low-viscosity VAE emulsion according to the weight ratio of 15:35: 35.
By adopting the technical scheme, the proportion of the raw materials of the water-based high-speed nozzle glue is optimized, so that the raw materials can better act in a synergistic manner, the finally prepared nozzle glue has better fluidity, and the nozzle glue is more suitable for high-speed spraying.
Preferably, the high-viscosity VAE emulsion is a DA142 emulsion, the medium-viscosity VAE emulsion is a DA143 emulsion, and the low-viscosity VAE emulsion is a DA146 emulsion.
By adopting the technical scheme, the VAE emulsions are further optimized, the adaptability among the VAE emulsions is stronger, and the VAE emulsions are easier to mutually disperse and combine in the production process of the nozzle adhesive.
Preferably, the polyvinyl alcohol solution has a solids content of 10 to 22%.
By adopting the technical scheme, the solution with lower solid content is selected for the polyvinyl alcohol, so that the polyvinyl alcohol is conveniently and fully dispersed in a mixed system, and is more easily contacted and combined with a vinyl acetate-ethylene copolymer chain in the VAE emulsion, and the occurrence probability of cohesiveness is reduced.
Preferably, the molecular weight of the polyvinyl alcohol in the polyvinyl alcohol solution is 120000-170000.
By adopting the technical scheme, the polyvinyl alcohol with high molecular weight is selected as the polyvinyl alcohol, so that the viscosity of the polyvinyl alcohol is increased, the film forming property of the nozzle connecting glue is improved, the strength and the toughness of a glue film are further improved, an ultrathin bonding film layer which is extremely thin but firmly bonded is obtained, and the bonding quality and the bonding appearance effect of cigarettes are improved.
Preferably, the bactericide is at least one of cason and potassium sorbate.
By adopting the technical scheme, because the contact probability of the part bonded by the nozzle adhesive and a human body is higher, the sterilizing agent adopts the kasong and the potassium sorbate, the very good sterilizing and corrosion preventing effects can be realized only by using a small amount, and the probability of harm of the sterilizing agent to the human body is reduced.
In a second aspect, the application provides a preparation method of a water-based high-speed nozzle adhesive, which adopts the following technical scheme:
the preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) uniformly mixing the VAE emulsion with water to obtain a mixed emulsion;
2) and uniformly mixing the mixed emulsion and the polyvinyl alcohol solution, then adding the bactericide, uniformly mixing, then adding the defoaming agent, and uniformly mixing to obtain the composite material.
By adopting the technical scheme, the VAE emulsion is firstly mixed with water, so that the VAE emulsion is diluted, the vinyl acetate-ethylene copolymer in the VAE emulsion is favorably and uniformly mixed with other raw materials, and the three VAE emulsions with different viscosities are also fully crosslinked and combined. On the basis, the mixed emulsion is mixed with the polyvinyl alcohol, so that the crosslinking combination of the polyvinyl alcohol and the vinyl acetate-ethylene copolymer is more sufficient, and the phenomenon of cohesiveness is reduced.
Preferably, the step 1) of mixing the VAE emulsion with water is to add the low-viscosity VAE emulsion, the medium-viscosity VAE emulsion and the high-viscosity VAE emulsion in sequence under stirring, then add water and stir for 3-5 h.
By adopting the technical scheme, because the vinyl acetate-ethylene copolymer in the VAE emulsion with high viscosity is relatively easy to be connected and cohered, the VAE emulsion with low viscosity is firstly stirred, then the VAE emulsion with medium viscosity is added and uniformly mixed, and then the VAE emulsion with high viscosity is added, under the condition of continuous stirring, the copolymer in the VAE emulsion with higher viscosity and more complex structure which is added later is more easily dispersed among the copolymers in the VAE emulsion with low viscosity which is added firstly, so that the cohering probability is reduced.
Preferably, after adding the defoaming agent and mixing uniformly, adding water to adjust the viscosity to 3000-5000.
By adopting the technical scheme, after the defoaming agent is added and uniformly mixed, water is added to adjust the viscosity to a certain range, the nozzle adhesive meeting the viscosity requirement can be prepared, and the quality stability of the prepared nozzle adhesive is improved.
Preferably, the polyvinyl alcohol solution is prepared by a process comprising the steps of: heating water to 55-65 ℃, then preserving heat for 1-2h, adding polyvinyl alcohol, and stirring for 3-5 h.
By adopting the technical scheme, when the polyvinyl alcohol is prepared, the water is heated to a certain temperature and is kept warm, so that the gas in the water can escape, the amount of the gas attached to the surface of the polyvinyl alcohol is reduced after the polyvinyl alcohol is added, the polyvinyl alcohol is fully contacted with the water and is easier to dissolve, and the amount of gas impurities in the polyvinyl alcohol solution is also reduced.
In summary, the present application has the following beneficial effects:
1. because the VAE emulsion is prepared by mixing the low-viscosity VAE emulsion, the medium-viscosity VAE emulsion and the high-viscosity VAE emulsion, the VAE emulsion is dispersed in water more uniformly by utilizing different crosslinking characteristics of vinyl acetate-ethylene polymers in different VAE emulsions, the fluidity of the emulsion is improved, and the VAE emulsion is more suitable for a high-speed spraying process. The subsequent addition of polyvinyl alcohol can graft with the long chain of vinyl acetate-ethylene copolymer in VAE emulsion, so that the strength and toughness of the bonding film layer when the nozzle adhesive is used are improved, and the stability of the nozzle adhesive is also improved.
2. The polyvinyl alcohol with the molecular weight of 120000-170000 is preferably adopted, so that the adhesion of the polyvinyl alcohol is improved, the film forming property of the finally prepared nozzle adhesive is improved, an adhesion film layer with very small thickness and very high adhesion strength is favorably obtained, and the adhesion quality is improved.
3. According to the preparation method of the water-based high-speed nozzle adhesive, the VAE emulsion and water are uniformly mixed and then are mixed with the polyvinyl alcohol, so that the VAE emulsions with different viscosities can be fully and uniformly mixed and are mutually crosslinked, and the VAE emulsions and the polyvinyl alcohol dispersion liquid are more uniform.
Detailed Description
The present application will be described in further detail with reference to specific embodiments.
The water-based high-speed nozzle adhesive is mainly prepared from water and the following raw materials in parts by weight: 83-86 parts of VAE emulsion, 8-11 parts of polyvinyl alcohol solution, 0.1-0.2 part of bactericide and 0.1-0.2 part of defoaming agent. Preferably, the water-based high-speed nozzle adhesive is mainly prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide and 0.1 part of defoaming agent. The VAE emulsion consists of high-viscosity VAE emulsion, medium-viscosity VAE emulsion and low-viscosity VAE emulsion according to the weight ratio of 10-15:30-40: 30-40; the viscosity of the high-viscosity VAE emulsion is 2500-; the viscosity of the medium-viscosity VAE emulsion is 1500-; the viscosity of the low-viscosity VAE emulsion is 180-2200mpa s. Preferably, the viscosity of the high-viscosity VAE emulsion, the medium-viscosity VAE emulsion and the low-viscosity VAE emulsion is reduced in sequence.
Preferably, the high-viscosity VAE emulsion has a solids content of 53-57%, the medium-viscosity VAE emulsion has a solids content of 58-62%, and the low-viscosity VAE emulsion has a solids content of 53-57%. Preferably, the high viscosity VAE emulsion has a solids content of 55%, the medium viscosity VAE emulsion has a solids content of 60%, and the low viscosity VAE emulsion has a solids content of 54.5%.
Preferably, the high viscosity VAE emulsion has a viscosity of 3000 mpa-s; the viscosity of the medium viscosity VAE emulsion is 2000mpa · s; the viscosity of the low viscosity VAE emulsion was 1000.
Preferably, the high-viscosity VAE emulsion is DA142 emulsion, the medium-viscosity VAE emulsion is DA143 emulsion, and the low-viscosity VAE emulsion is DA146 emulsion, which are all produced by chemical engineering (Jiangsu) Co.
The solid content of the polyvinyl alcohol solution is 10-22%.
The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution is 100000-150000. The molecular weight of the polyvinyl alcohol is preferably 150000.
The bactericide is at least one of cason and potassium sorbate. Preferably, the bactericide is prepared by mixing the kaempferol and the potassium sorbate in a mass ratio of 1: 1.
The defoaming agent is an organic silicon defoaming agent or a polyether modified organic silicon defoaming agent. Preferably, the polyether modified silicone defoaming agent is polyether modified dimethyl siloxane.
Furthermore, the raw material also comprises 0.1 to 0.2 weight part of sodium alginate. Furthermore, the raw material also comprises 0.05 to 0.08 weight part of diatomite.
Further, the raw materials also comprise 0.05 to 0.1 weight part of a leveling agent, and preferably, the leveling agent is a fluorine modified acrylic leveling agent. Further preferably, the leveling agent is a BASF Irgaflow 100 fluorine modified acrylic leveling agent.
Further, the raw materials also comprise 0.05 to 0.08 weight part of film forming agent, and the film forming agent is prepared by the method comprising the following steps: reacting 5-norbornene-2-carboxylic acid with thionyl chloride to form a norbornene derivative, then polymerizing the norbornene derivative with polyethylene glycol to form a polymer intermediate, and polymerizing the polymer intermediate with 5-vinyl-2-norbornene. The mass ratio of the polymerization intermediate to 5-vinyl-2-norbornene is 70-90: 16-28. Preferably, the mass ratio of the polymerization intermediate to 5-vinyl-2-norbornene is 90: 16.
The mass ratio of the polyethylene glycol to the norbornene derivative is 4-6: 3-4. Preferably, the mass ratio of polyethylene glycol to norbornene derivative is 4-6: 3. Further preferably, the mass ratio of polyethylene glycol to norbornene derivative is 2: 1.
The number average molecular weight of the polyethylene glycol is 200-. More preferably, the polyethylene glycol has a number average molecular weight of 600. The polyethylene glycol is polyethylene glycol 400 or polyethylene glycol 600. Further preferably, the polyethylene glycol is polyethylene glycol 600.
During the reaction of polyethylene glycol and norbornene derivative, triethylamine is also added. The mass ratio of the triethylamine to the norbornene derivative is 0.7-1: 3-4. Preferably, the mass ratio of triethylamine to norbornene derivative is 0.7 to 1: 3. Further preferably, the mass ratio of triethylamine to norbornene derivative is 1: 3.
Furthermore, the raw material also comprises 0.01 to 0.03 weight part of cosolvent, wherein the cosolvent is any one of N, N-dimethylformamide and tetrahydrofuran.
Further, the raw material also comprises 0.03-0.05 weight part of stabilizer, wherein the stabilizer is any one of calcium stearoyl lactylate, sodium caseinate, propylene glycol alginate and gluconic acid-delta-lactone. The stabilizer is prepared from at least one of calcium stearoyl lactylate, sodium caseinate and propylene glycol alginate and gluconic acid-delta-lactone in a mass ratio of 1-3: 3-5, mixing. Further preferably, the stabilizer is formed by mixing calcium stearoyl lactylate, sodium caseinate and gluconic acid-delta-lactone in a mass ratio of 1-2:0.5-1: 3-5. Further preferably, the stabilizer is formed by mixing calcium stearoyl lactylate, sodium caseinate and glucono-delta-lactone in a mass ratio of 1.5:0.5: 4.5. The stabilizer adopts the gluconic acid-delta-lactone as a main component of the stabilizer and is matched with other stabilizers, wherein the gluconic acid-delta-lactone has better water solubility and is easier to uniformly disperse in glue, and the gluconic acid-delta-lactone has better solidification effect and is convenient for glue layer formation sprayed to a bonding position by matching with the thickening effect of other stabilizers.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) uniformly mixing the VAE emulsion with water to obtain a mixed emulsion;
2) and uniformly mixing the mixed emulsion and the polyvinyl alcohol solution, then adding the bactericide, uniformly mixing, then adding the defoaming agent, and uniformly mixing to obtain the composite material.
The step 1) of mixing the VAE emulsion with water is to sequentially add the low-viscosity VAE emulsion, the medium-viscosity VAE emulsion and the high-viscosity VAE emulsion under the stirring condition, then add water and stir for 3-5 h. The stirring when mixing the VAE emulsion and water uniformly is carried out at the rotation speed of 200-270rpm for 3-5 h. Preferably, the stirring time is 4h after the addition of water.
In the step 2), the mixed emulsion and the polyvinyl alcohol solution are uniformly mixed for 3 to 5 hours. Preferably, the mixing of the mixed emulsion and the polyvinyl alcohol solution is to stir the mixed emulsion and the polyvinyl alcohol solution at the rotation speed of 300-. The stirring time is preferably 4 h.
The polyvinyl alcohol solution is prepared by a method comprising the following steps: heating water to 55-65 ℃, then preserving heat for 1-2h, adding polyvinyl alcohol, and stirring for 3-5 h. The stirring speed is 600-800 rpm. Preferably, the temperature of the water is raised to 60 ℃ and kept for 1 h.
Adding the bactericide in the step 2), uniformly mixing, and stirring for 1-2 h; adding the defoaming agent, and stirring for 0.5-1.5 h. Preferably, the bactericide is added and uniformly mixed in the step 2) and stirred for 1.2 h; adding the defoaming agent and uniformly mixing, and stirring for 1 h. The stirring speed when the mixed emulsion and the bactericide are uniformly mixed is 150-180 rpm. The stirring speed when the defoaming agent is added and mixed uniformly is 100-150 rpm.
Adding a defoaming agent, mixing uniformly, adding water to adjust the viscosity to 3000-5000.
Preferably, sodium alginate is added at the same time as the bactericide is added. Further, diatomite is added at the same time of adding the defoaming agent. Further preferably, a leveling agent is added at the same time as the defoaming agent is added. Further preferably, after the defoaming agent is added and uniformly mixed, the stabilizing agent is added and stirred for 0.3 to 0.5 hour at the rotating speed of 60 to 80 rpm. Preferably, the film forming agent is added at the same time when the stabilizing agent is added. Further preferably, a cosolvent is added at the same time as the stabilizer is added.
The preparation method of the film forming agent comprises the following steps:
a) carrying out reflux reaction on 5-norbornene-2-carboxylic acid and thionyl chloride under inert atmosphere to obtain a norbornene derivative; mixing norbornene derivatives and polyethylene glycol in a solvent, and then reacting in an inert atmosphere to obtain a polymerization intermediate;
b) mixing the polymer intermediate prepared in the step a) with 5-vinyl-2-norbornene in a solvent, and then carrying out polymerization reaction under an inert atmosphere to obtain the film-forming agent.
The preparation method comprises the steps of reacting 5-norbornene-2-carboxylic acid with thionyl chloride to obtain norbornene derivatives with acyl chloride groups, combining the norbornene derivatives with the polyethylene glycol to generate a polymerization intermediate, and then carrying out polymerization reaction on the polymerization intermediate and 5-vinyl-2-norbornene under the action of a catalyst to obtain a film forming agent which has a structure that norbornene structures and polyethylene glycol structures are sequentially distributed in a staggered manner, so that long-chain structures are easily formed, and further, the film forming agent has better film forming property, is favorable for uniform dispersion of nozzle glue, forms a very thin film layer after spraying, and is uniform in bonding and high in bonding strength.
The molar ratio of 5-norbornene-2-carboxylic acid to thionyl chloride in step a) is from 1:8 to 10. The amount of the substance of the thionyl chloride is far greater than that of the substance of the 5-norbornene-2-carboxylic acid, so that the carboxyl on the 5-norbornene-2-carboxylic acid is fully converted into acyl chloride groups, and the terminal groups at two ends of a polymer chain of the polyethylene glycol can be ensured to react more completely in the subsequent reaction process.
Preferably, the molar ratio of 5-norbornene-2-carboxylic acid to thionyl chloride is 1: 9. The reflux in the step a) is stirring reflux at 70-80 ℃ for 8-10 h. Preferably, the reflux is at 75-80 deg.C with stirring and reflux for 8 h. Further preferably, the reflux is a stirred reflux at 75 ℃ for 8 h.
The reaction of polyethylene glycol with norbornene derivative in step a) is carried out at 70-75 deg.C under stirring and reflux for 15-20 h. Preferably, the reaction of polyethylene glycol with norbornene derivative is carried out at 70 ℃ under stirring and reflux for 18 h. During the reaction of polyethylene glycol and norbornene derivative, triethylamine is also added. The mass ratio of the triethylamine to the norbornene derivative is 0.7-1: 3-4. Preferably, the mass ratio of triethylamine to norbornene derivative is 0.7 to 1: 3. Further preferably, the mass ratio of triethylamine to norbornene derivative is 1: 3.
After the reaction of polyethylene glycol and norbornene derivative, cooling, filtering, mixing the solid with sufficient amount of ether, adding sufficient amount of saturated sodium bicarbonate solution, mixing, separating, and vacuum drying the organic phase to obtain the intermediate. The temperature for vacuum drying was 30 ℃.
The mass ratio of the polyethylene glycol to the norbornene derivative is 4-6: 3-4. Preferably, the mass ratio of polyethylene glycol to norbornene derivative is 4-6: 3. Further preferably, the mass ratio of polyethylene glycol to norbornene derivative is 2: 1.
The number average molecular weight of the polyethylene glycol is 200-. More preferably, the polyethylene glycol has a number average molecular weight of 600. The polyethylene glycol is polyethylene glycol 400 or polyethylene glycol 600. Further preferably, the polyethylene glycol is polyethylene glycol 600.
The mass ratio of the polymerization intermediate to 5-vinyl-2-norbornene in the step b) is 70-90: 16-28. Preferably, the mass ratio of the polymerization intermediate to 5-vinyl-2-norbornene is 90: 16. Adding a catalyst when the polymerization intermediate reacts with the 5-vinyl-2-norbornene. The catalyst is preferably a Grubbs2 catalyst, a Grubbs second generation catalyst. The mass ratio of the catalyst to the 5-vinyl-2-norbornene is 1: 16-28. Preferably, the mass ratio of the catalyst to 5-vinyl-2-norbornene is 1: 16. A solvent is also added when the polymerization intermediate reacts with 5-vinyl-2-norbornene. The polymerization intermediate and the 5-vinyl-2-norbornene react for 6 to 8 hours in a mixed reaction under an inert atmosphere. Preferably, the reaction time is 7 h. After the reaction, ethyl vinyl ether is added to terminate the reaction, after cooling, ethyl ether is added to mix, the mixture is filtered, washed by ethylene and then dried in vacuum. The temperature for vacuum drying was 30 ℃.
The inert atmosphere is nitrogen atmosphere or argon atmosphere. Preferably, the inert atmosphere is a nitrogen atmosphere. The solvent is dichloromethane
Example 1
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 83 parts of VAE emulsion, 11 parts of polyvinyl alcohol solution, 0.2 part of bactericide and 0.2 part of defoaming agent. The amount of water included 5 parts water and a small amount of water to adjust the viscosity after the water-based high speed nipple glue was made.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 13:30:40, wherein the solid content of the DA142 emulsion is 53%, and the viscosity is 2500mpa & s; the solid content of the DA143 emulsion is 58%, and the viscosity is 1500mpa · s; the DA146 emulsion had a solids content of 53% and a viscosity of 500. The polyvinyl alcohol solution had a solids content of 10%. The molecular weight of the polyvinyl alcohol in the polyvinyl alcohol solution is 100000. The bactericide is Kathon. The defoaming agent is an organic silicon defoaming agent.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) starting a stirrer of the reaction kettle, stirring at a rotating speed of 200rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 5 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 55 ℃, then preserving heat for 2 hours, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 600rpm for 5 hours until the polyvinyl alcohol is completely dissolved, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 1), stirring at the rotating speed of 300rpm for 5h, then adding a bactericide, then stirring at the rotating speed of 150rpm for 2h, then adding a defoaming agent, stirring at the rotating speed of 100rpm for 1h, and then adding water to adjust the viscosity of the mixture to 3000-5000, thus obtaining the water-based emulsion.
Example 2
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 86 parts of VAE emulsion, 8 parts of polyvinyl alcohol solution, 0.1 part of bactericide and 0.1 part of defoaming agent. The amount of water included 3 parts water and a small amount of water to adjust the viscosity after the water-based high speed nipple glue was made.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:40:31, wherein the solid content of the DA142 emulsion is 53%, and the viscosity is 2500mpa & s; the solid content of the DA143 emulsion is 58%, and the viscosity is 1500mpa · s; the DA146 emulsion had a solids content of 53% and a viscosity of 500. The polyvinyl alcohol solution had a solids content of 22%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000. The bactericide is Kathon. The defoaming agent is an organic silicon defoaming agent.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) starting a stirrer of the reaction kettle, stirring at a rotating speed of 270rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 3 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 65 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 800rpm for 3h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 1), stirring for 3h at the rotating speed of 360rpm, then adding a bactericide, then stirring for 1h at the rotating speed of 180rpm, then adding a defoaming agent, stirring for 0.5h at the rotating speed of 150rpm, and then adding water to adjust the viscosity of the mixture to 3000-5000-.
Example 3
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide and 0.1 part of defoaming agent. The amount of water was 5 parts.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:35:35, wherein the solid content of the DA142 emulsion is 55%, and the viscosity is 3000mpa & s; the DA143 emulsion has a solid content of 60% and a viscosity of 2000mPa & s; the DA146 emulsion had a solids content of 54.5% and a viscosity of 1000. The polyvinyl alcohol solution had a solids content of 15%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000. The bactericide is Kathon. The defoaming agent is an organic silicon defoaming agent.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) starting a stirrer of the reaction kettle, stirring at a rotating speed of 250rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 4 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 60 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 720rpm for 4h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 1), stirring at the rotating speed of 330rpm for 4 hours, then adding a bactericide, then stirring at the rotating speed of 160rpm for 1.2 hours, then adding a defoaming agent, and stirring at the rotating speed of 120rpm for 1 hour to obtain the emulsion.
Example 4
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide, 0.1 part of defoaming agent and 0.15 part of sodium alginate. The amount of water was 5 parts.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:35:35, wherein the solid content of the DA142 emulsion is 55%, and the viscosity is 3000mpa & s; the DA143 emulsion has a solid content of 60% and a viscosity of 2000mPa & s; the DA146 emulsion had a solids content of 54.5% and a viscosity of 1000. The polyvinyl alcohol solution had a solids content of 15%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000. The bactericide is Kathon. The defoaming agent is an organic silicon defoaming agent.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) starting a stirrer of the reaction kettle, stirring at a rotating speed of 250rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 4 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 60 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 720rpm for 4h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 1), stirring at the rotating speed of 330rpm for 4 hours, then adding a bactericide and sodium alginate, stirring at the rotating speed of 160rpm for 1.2 hours, then adding a defoaming agent, and stirring at the rotating speed of 120rpm for 1 hour to obtain the antibacterial emulsion.
Example 5
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide, 0.1 part of defoaming agent, 0.1 part of sodium alginate and 0.08 part of diatomite. The amount of water was 5 parts.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:35:35, wherein the solid content of the DA142 emulsion is 55%, and the viscosity is 3000mpa & s; the DA143 emulsion has a solid content of 60% and a viscosity of 2000mPa & s; the DA146 emulsion had a solids content of 54.5% and a viscosity of 1000. The polyvinyl alcohol solution had a solids content of 15%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000. The bactericide is Kathon. The defoaming agent is an organic silicon defoaming agent.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) starting a stirrer of the reaction kettle, stirring at a rotating speed of 250rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 4 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 60 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 720rpm for 4h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 1), stirring at the rotating speed of 330rpm for 4 hours, then adding a bactericide and sodium alginate, stirring at the rotating speed of 160rpm for 1.2 hours, then adding a defoaming agent and diatomite, and stirring at the rotating speed of 120rpm for 1 hour to obtain the nano-emulsion.
Example 6
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide, 0.1 part of defoaming agent, 0.2 part of sodium alginate, 0.08 part of diatomite and 0.05 part of stabilizer. The amount of water was 5 parts.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:35:35, wherein the solid content of the DA142 emulsion is 55%, and the viscosity is 3000mpa & s; the DA143 emulsion has a solid content of 60% and a viscosity of 2000mPa & s; the DA146 emulsion had a solids content of 54.5% and a viscosity of 1000. The polyvinyl alcohol solution had a solids content of 15%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000. The bactericide is Kathon. The defoaming agent is polyether modified organic silicon defoaming agent. The stabilizer is calcium stearoyl lactate.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) starting a stirrer of the reaction kettle, stirring at a rotating speed of 250rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 4 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 60 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 720rpm for 4h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 1), stirring at a rotating speed of 330rpm for 4 hours, then adding a bactericide and sodium alginate, then stirring at a rotating speed of 160rpm for 1.2 hours, then adding a defoaming agent and diatomite, stirring at a rotating speed of 120rpm for 1 hour, then adding a stabilizer, and stirring at a rotating speed of 70rpm for 10 minutes to obtain the antibacterial emulsion.
Example 7
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide, 0.1 part of defoaming agent, 0.1 part of sodium alginate, 0.08 part of diatomite, 0.03 part of stabilizer and 0.1 part of film-forming agent. The amount of water was 5 parts.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:35:35, wherein the solid content of the DA142 emulsion is 55%, and the viscosity is 3000mpa & s; the DA143 emulsion has a solid content of 60% and a viscosity of 2000mPa & s; the DA146 emulsion had a solids content of 54.5% and a viscosity of 1000. The polyvinyl alcohol solution had a solids content of 15%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000.
The bactericide is prepared by mixing the kasong and the potassium sorbate in a mass ratio of 1: 1. The defoaming agent is polyether modified organic silicon defoaming agent. The stabilizer is formed by mixing calcium stearoyl lactylate and gluconic acid-delta-lactone according to the mass ratio of 1: 3.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) adding 5-norbornene-2-carboxylic acid and thionyl chloride into a reaction vessel according to a molar ratio of 1:10, stirring and refluxing for 10 hours at 75 ℃ in a nitrogen atmosphere, and then distilling under reduced pressure to obtain a residue which is a norbornene derivative; then adding polyethylene glycol 400 and diethylamine into the above-mentioned liquid after reduced pressure distillation according to the mass ratio of 4:0.7:3 with norbornene derivative, stirring and refluxing for 15h at 75 deg.C under nitrogen atmosphere, cooling and filtering; adding sufficient diethyl ether into the solid, uniformly stirring, then adding sufficient saturated sodium bicarbonate solution, uniformly stirring, standing for liquid separation, and carrying out vacuum drying on an organic phase at the temperature of 30 ℃ to obtain a polymerization intermediate;
adding the polymerization intermediate, 5-vinyl-2-norbornene and Grubbs2 catalyst into dichloromethane according to the mass ratio of 70:28:1, mixing and stirring for reaction for 6 hours under the nitrogen atmosphere, then adding a small amount of ethyl vinyl ether to terminate the reaction, cooling, adding diethyl ether for mixing, then filtering, washing with diethyl ether, and then drying in vacuum at 30 ℃ to obtain a film-forming agent;
2) starting a stirrer of the reaction kettle, stirring at a rotating speed of 250rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 4 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 60 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 720rpm for 4h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 2), stirring at a rotating speed of 330rpm for 4 hours, then adding a bactericide and sodium alginate, then stirring at a rotating speed of 160rpm for 1.2 hours, then adding a defoaming agent and diatomite, stirring at a rotating speed of 120rpm for 1 hour, then adding a film forming agent and a stabilizing agent, and stirring at a rotating speed of 70rpm for 10 minutes to obtain the aqueous emulsion.
Example 8
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide, 0.1 part of defoaming agent, 0.1 part of sodium alginate, 0.05 part of diatomite, 0.03 part of stabilizer, 0.05 part of film-forming agent and 0.1 part of flatting agent. The amount of water was 5 parts.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:35:35, wherein the solid content of the DA142 emulsion is 55%, and the viscosity is 3000mpa & s; the DA143 emulsion has a solid content of 60% and a viscosity of 2000mPa & s; the DA146 emulsion had a solids content of 54.5% and a viscosity of 1000. The polyvinyl alcohol solution had a solids content of 15%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000. The bactericide is prepared by mixing the kasong and the potassium sorbate in a mass ratio of 1: 1. The defoaming agent is polyether modified organic silicon defoaming agent. The stabilizer is prepared by mixing calcium stearoyl lactylate, sodium caseinate and gluconic acid-delta-lactone according to the mass ratio of 1.5:0.5: 4.5.
The film forming agent is prepared by the following steps: reacting 5-norbornene-2-carboxylic acid with thionyl chloride to form a norbornene derivative, then polymerizing the norbornene derivative with polyethylene glycol, and polymerizing the resulting polymer with 5-vinyl-2-norbornene.
The leveling agent is a BASF Irgaflow 100 fluorine modified acrylic acid leveling agent.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) adding 5-norbornene-2-carboxylic acid and thionyl chloride into a reaction vessel according to a molar ratio of 1:8, stirring and refluxing for 8 hours at 80 ℃ in a nitrogen atmosphere, and then distilling under reduced pressure to obtain a residue which is a norbornene derivative; then adding polyethylene glycol 600 and triethylamine according to the mass ratio of 6:1:3 to the norbornene derivative into the liquid obtained after reduced pressure distillation, stirring and refluxing for 20 hours at 70 ℃ in a nitrogen atmosphere, cooling and filtering; adding sufficient diethyl ether into the solid, uniformly stirring, then adding sufficient saturated sodium bicarbonate solution, uniformly stirring, standing for liquid separation, and carrying out vacuum drying on an organic phase at the temperature of 30 ℃ to obtain a polymerization intermediate;
adding the polymerization intermediate, 5-vinyl-2-norbornene and Grubbs2 catalyst into dichloromethane according to a mass ratio of 90:16:1, mixing and stirring for reaction for 8 hours under a nitrogen atmosphere, then adding a small amount of ethyl vinyl ether to terminate the reaction, cooling, adding diethyl ether to mix, then filtering, washing with diethyl ether, and then drying in vacuum at 30 ℃ to obtain a film-forming agent;
2) starting a stirrer of the reaction kettle, stirring at a rotating speed of 250rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 4 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 60 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 720rpm for 4h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 2), stirring at a rotating speed of 330rpm for 4 hours, then adding a bactericide and sodium alginate, then stirring at a rotating speed of 160rpm for 1.2 hours, then adding a defoaming agent, diatomite and a leveling agent, stirring at a rotating speed of 120rpm for 1 hour, then adding a film forming agent and a stabilizing agent, and stirring at a rotating speed of 70rpm for 10 minutes to obtain the aqueous emulsion.
Example 9
The water-based high-speed nozzle adhesive of the embodiment is prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide, 0.1 part of defoaming agent, 0.1 part of sodium alginate, 0.05 part of diatomite, 0.03 part of stabilizer, 0.05 part of film-forming agent, 0.05 part of flatting agent and 0.03 part of cosolvent. The amount of water was 5 parts.
The VAE emulsion comprises DA142 emulsion, DA143 emulsion and DA146 emulsion according to the weight ratio of 15:35:35, wherein the solid content of the DA142 emulsion is 55%, and the viscosity is 3000mpa & s; the DA143 emulsion has a solid content of 60% and a viscosity of 2000mPa & s; the DA146 emulsion had a solids content of 54.5% and a viscosity of 1000. The polyvinyl alcohol solution had a solids content of 15%. The molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution was 150000. The bactericide is prepared by mixing the kasong and the potassium sorbate in a mass ratio of 1: 1. The defoaming agent is polyether modified organic silicon defoaming agent.
The film forming agent is prepared by the following steps: reacting 5-norbornene-2-carboxylic acid with thionyl chloride to form a norbornene derivative, then polymerizing the norbornene derivative with polyethylene glycol, and polymerizing the resulting polymer with 5-vinyl-2-norbornene.
The stabilizer is prepared by mixing calcium stearoyl lactylate, sodium caseinate and gluconic acid-delta-lactone according to the mass ratio of 1.5:0.5: 4.5. The leveling agent is a BASF Irgaflow 100 fluorine modified acrylic acid leveling agent. The cosolvent is N, N-dimethylformamide.
The preparation method of the water-based high-speed nozzle adhesive comprises the following steps:
1) adding 5-norbornene-2-carboxylic acid and thionyl chloride into a reaction vessel according to a molar ratio of 1:9, stirring and refluxing for 8 hours at 75 ℃ in a nitrogen atmosphere, and then distilling under reduced pressure to obtain a residue which is a norbornene derivative; then adding polyethylene glycol 600 and triethylamine according to the mass ratio of 6:1:3 to the norbornene derivative into the liquid obtained after reduced pressure distillation, stirring and refluxing for 18h at 70 ℃ in a nitrogen atmosphere, cooling and filtering; adding sufficient diethyl ether into the solid, uniformly stirring, then adding sufficient saturated sodium bicarbonate solution, uniformly stirring, standing for liquid separation, and carrying out vacuum drying on an organic phase at the temperature of 30 ℃ to obtain a polymerization intermediate;
adding the polymerization intermediate, 5-vinyl-2-norbornene and Grubbs2 catalyst into dichloromethane according to a mass ratio of 90:16:1, mixing and stirring for reaction for 7 hours under a nitrogen atmosphere, then adding a small amount of ethyl vinyl ether to terminate the reaction, cooling, adding diethyl ether to mix, then filtering, washing with diethyl ether, and then drying in vacuum at 30 ℃ to obtain a dispersing agent;
2) starting a stirrer of the reaction kettle, stirring at a rotating speed of 250rpm, slowly adding the low-viscosity VAE emulsion from a feeding port above the reaction kettle, adding the medium-viscosity VAE emulsion after the low-viscosity VAE emulsion is added, adding the high-viscosity VAE emulsion after the medium-viscosity VAE emulsion is added, adding water after the high-viscosity VAE emulsion is added, and continuously stirring for 4 hours to obtain a mixed emulsion;
adding water into another reaction kettle, heating to 60 ℃, then preserving heat for 1h, starting a stirrer, slowly adding polyvinyl alcohol solid from a feeding port above the reaction kettle, stirring at the rotating speed of 720rpm for 4h, completely dissolving the polyvinyl alcohol, discharging from a discharging port below the reaction kettle to obtain polyvinyl alcohol solution, and storing in a constant-temperature storehouse for later use;
2) adding a polyvinyl alcohol solution into the mixed emulsion obtained in the step 2), stirring at a rotating speed of 330rpm for 4 hours, then adding a bactericide and sodium alginate, stirring at a rotating speed of 160rpm for 1.2 hours, then adding a defoaming agent, diatomite and a leveling agent, stirring at a rotating speed of 120rpm for 1 hour, then adding a film forming agent, a stabilizing agent and a cosolvent, and stirring at a rotating speed of 70rpm for 10 minutes to obtain the aqueous emulsion.
Test examples
The water-based high-speed mouth-connecting glue of examples 1-9 was measured for viscosity, particle size, dilution stability and minimum film-forming temperature according to the test methods of YC/T188-2004 "high-speed cigarette adhesive", initial adhesion was measured according to GB/T31125-2014 "Ring method for adhesive tape initial adhesion test method", stability was measured according to GB/T7123.1-2002 "determination of adhesive pot life", and the test results are shown in Table 1.
TABLE 1 test results of the properties of the nozzle rubber in examples 1 to 9
Figure GDA0003423775250000161
Figure GDA0003423775250000171
As can be seen from Table 1, the water-based high-speed nozzle adhesive has moderate viscosity, small granularity and good fluidity and is suitable for being used by a high-speed cigarette making machine. Tests show that the water-based high-speed nozzle adhesive is suitable for the high-speed production requirements of cigarette making machines with over 16000 cigarettes/min, has good adhesive coating continuity, is not easy to generate bubbles, does not generate a tiny adhesive breaking layer, and does not generate the adhesive flying phenomenon. The water-based high-speed nozzle adhesive has the advantages of low film forming temperature, good adaptability, high initial viscosity and high bonding strength. In addition, the water-based high-speed nozzle adhesive has better dilution stability and storage stability.

Claims (8)

1. A water-based high-speed nozzle adhesive is characterized in that: the water-based paint is mainly prepared from water and the following raw materials in parts by weight: 83-86 parts of VAE emulsion, 8-11 parts of polyvinyl alcohol solution, 0.1-0.2 part of bactericide and 0.1-0.2 part of defoaming agent; the VAE emulsion consists of high-viscosity VAE emulsion, medium-viscosity VAE emulsion and low-viscosity VAE emulsion according to the weight ratio of 10-15:30-40: 30-40; the viscosity of the high-viscosity VAE emulsion is 2500-3700mpa & s; the viscosity of the medium-viscosity VAE emulsion is 1500-2500mpa & s; the viscosity of the low-viscosity VAE emulsion is 180-2200 mpa-s;
the high-viscosity VAE emulsion is DA142 emulsion, the medium-viscosity VAE emulsion is DA143 emulsion, and the low-viscosity VAE emulsion is DA146 emulsion; the VAE emulsion is produced by chemical engineering of Dalian Kagaku (Jiangsu) Co.Ltd;
the solid content of the polyvinyl alcohol solution is 10-22%.
2. The water-based high-speed nozzle adhesive according to claim 1, wherein: the water-based high-speed nozzle connecting glue is mainly prepared from water and the following raw materials in parts by weight: 85 parts of VAE emulsion, 10 parts of polyvinyl alcohol solution, 0.1 part of bactericide and 0.1 part of defoaming agent; the VAE emulsion consists of high-viscosity VAE emulsion, medium-viscosity VAE emulsion and low-viscosity VAE emulsion according to the weight ratio of 15:35: 35.
3. The water-based high-speed nozzle adhesive as claimed in claim 2, wherein: the molecular weight of the polyvinyl alcohol in the polyvinyl alcohol solution is 120000-170000.
4. The water-based high-speed nozzle adhesive according to claim 1 or 2, wherein: the bactericide is at least one of cason and potassium sorbate.
5. A method for preparing the water-based high-speed nozzle adhesive according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
1) uniformly mixing the VAE emulsion with water to obtain a mixed emulsion;
2) and uniformly mixing the mixed emulsion and the polyvinyl alcohol solution, then adding the bactericide, uniformly mixing, then adding the defoaming agent, and uniformly mixing to obtain the composite material.
6. The method for preparing the water-based high-speed nozzle adhesive according to claim 5, wherein the method comprises the following steps: the step 1) of mixing the VAE emulsion with water is to sequentially add the low-viscosity VAE emulsion, the medium-viscosity VAE emulsion and the high-viscosity VAE emulsion under the stirring condition, then add water and stir for 3-5 h.
7. The method for preparing the water-based high-speed nozzle adhesive according to claim 5, wherein the method comprises the following steps: adding a defoaming agent in the step 2), uniformly mixing, adding water to adjust the viscosity to 3000-.
8. The method for preparing the water-based high-speed nozzle adhesive according to claim 5, wherein the method comprises the following steps: the polyvinyl alcohol solution in the step 2) is prepared by a method comprising the following steps: heating water to 55-65 ℃, then preserving heat for 1-2h, adding polyvinyl alcohol, and stirring for 3-5 h.
CN202010866413.3A 2020-08-25 2020-08-25 Water-based high-speed nozzle connecting adhesive and preparation method thereof Active CN112011292B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010866413.3A CN112011292B (en) 2020-08-25 2020-08-25 Water-based high-speed nozzle connecting adhesive and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010866413.3A CN112011292B (en) 2020-08-25 2020-08-25 Water-based high-speed nozzle connecting adhesive and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112011292A CN112011292A (en) 2020-12-01
CN112011292B true CN112011292B (en) 2022-03-08

Family

ID=73503985

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010866413.3A Active CN112011292B (en) 2020-08-25 2020-08-25 Water-based high-speed nozzle connecting adhesive and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112011292B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113416507B (en) * 2021-07-14 2023-02-10 湖北恒阳科技发展有限公司 Ultrahigh-speed nozzle connecting adhesive and preparation method thereof
CN116376475A (en) * 2023-04-17 2023-07-04 长沙乐远化工科技有限公司 Quick-drying high-speed lap adhesive and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105018004A (en) * 2015-06-25 2015-11-04 云南中烟工业有限责任公司 Holder adhesive for cellulose acetate cigarette tipping paper
CN105567133A (en) * 2016-01-13 2016-05-11 华威化工（上海）有限公司 Ultra-high-speed cigarette mouthpiece adhesive and preparation method thereof
CN107267090A (en) * 2017-07-09 2017-10-20 云南中烟工业有限责任公司 A kind of cellulose acetate cigarette tipping paper is with connecing mouth glue
CN109251703A (en) * 2018-08-06 2019-01-22 常德市芙蓉实业发展有限责任公司 A kind of anti-shearing cigarette is with connecing mouth glue and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105018004A (en) * 2015-06-25 2015-11-04 云南中烟工业有限责任公司 Holder adhesive for cellulose acetate cigarette tipping paper
CN105567133A (en) * 2016-01-13 2016-05-11 华威化工（上海）有限公司 Ultra-high-speed cigarette mouthpiece adhesive and preparation method thereof
CN107267090A (en) * 2017-07-09 2017-10-20 云南中烟工业有限责任公司 A kind of cellulose acetate cigarette tipping paper is with connecing mouth glue
CN109251703A (en) * 2018-08-06 2019-01-22 常德市芙蓉实业发展有限责任公司 A kind of anti-shearing cigarette is with connecing mouth glue and preparation method thereof

Also Published As

Publication number Publication date
CN112011292A (en) 2020-12-01

Similar Documents

Publication Publication Date Title
CN112011292B (en) Water-based high-speed nozzle connecting adhesive and preparation method thereof
CN102372885B (en) A kind of high viscosity polyvinyl acetate emulsion and preparation method thereof
CA1334547C (en) Process for the production of a dry product suitable as a paste base
CN112724708B (en) Surface treatment method of nano calcium carbonate for impact-resistant automobile chassis coating
CN103601837B (en) A kind of polyacrylate dispersion and preparation method
CN103524696A (en) Silicane modified sulfonic waterborne polyurethane emulsion and preparation method thereof
CN107501635A (en) A kind of preparation method of graphene/sodium alginate composite
CN101457499A (en) Surface sizing agent and its production method
US3740369A (en) Low viscosity solution of fluoropolymer due to the use of polar organic compounds
CN114181607A (en) Waterborne polyurethane waterproof coating and cold preparation process thereof
CN111393966A (en) Solvent-free silane-terminated modified polyether three-proofing paint and preparation method thereof
CN101595534A (en) Waterborne conductive compositions
CN109943120B (en) Wall cloth base film and preparation process thereof
CN109988322A (en) Water-based fluoropolymer emulsion, preparation method and applications
CN104497154A (en) Preparation method of hydroxy butyl starch ether or hydroxy butyl modified starch ether
JP4488561B2 (en) Synthetic resin emulsion type adhesive
CN103992435B (en) A kind of synthetic method of Vltra tears graft acrylic acid methyl esters/vinyl acetate sand-fixation agent
CN108997833B (en) Water-resistant composite modified polyvinyl alcohol water-based ink and preparation method thereof
CN108893042A (en) A kind of wear-resisting scratch-resisting type environment protecting water-based paint and preparation method thereof
WO2023103093A1 (en) Preparation method and application for water-based coating containing carboxymethyl modified cellulose nanofibers
US2671065A (en) Polyvinyl acetate dispersion and method of making utilizing polyacrylic acid and monomer soluble and monomer insoluble catalyst
CN110306364A (en) A kind of starch complex thickener and preparation method thereof
CN112011229B (en) Water-based eurytopic packaging adhesive and preparation method thereof
CN107916027A (en) A kind of slurry of the ink-jet on packaging material
CN110408345B (en) High-stability wallpaper adhesive

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant