CN114774058A - Preparation method of waterborne polyurethane adhesive - Google Patents

Preparation method of waterborne polyurethane adhesive Download PDF

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Publication number
CN114774058A
CN114774058A CN202210624885.7A CN202210624885A CN114774058A CN 114774058 A CN114774058 A CN 114774058A CN 202210624885 A CN202210624885 A CN 202210624885A CN 114774058 A CN114774058 A CN 114774058A
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stirring
parts
polyurethane adhesive
polyether polyol
grinding
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黄君涛
钱呈辉
周扬勇
徐航
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/329—Hydroxyamines containing aromatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a preparation method of a water-based polyurethane adhesive, belongs to the technical field of adhesive production, and solves the technical problems of low preparation efficiency, high cost, poor bonding effect and the like of the existing water-based polyurethane adhesive. The preparation method of the waterborne polyurethane adhesive comprises the following steps: (8.5-9.5), the part A and the part B are mixed and produced, and a multistage stirring device is adopted for mixing production, so that the production efficiency is high, and the energy consumption is low; the raw material matching is scientific and reasonable, and the bonding effect is obvious; the multistage stirring device has a compact structure, occupies a small area, realizes simultaneous production of A, B parts, and has high stirring efficiency and low energy consumption; the constant-temperature stirring is guaranteed by the cooperation of the heating stirring kettle, the control heater and the first heat-preservation cylinder, the temperature-adjusting stirring tank and the second heat-preservation cylinder are matched, the material in the temperature-adjusting stirring tank is effectively and quickly cooled, the mixing stability is guaranteed, the stirring and mixing are uniform, the material mixing efficiency is improved, and the production efficiency is high.

Description

Preparation method of waterborne polyurethane adhesive
Technical Field
The invention belongs to the technical field of adhesives, and relates to a preparation method of a water-based polyurethane adhesive.
Background
The application of the waterborne polyurethane adhesive is wider and wider. However, the whole polyurethane adhesive industry still mainly adopts a solvent type, and the research on the water-based polyurethane adhesive is rapidly developed along with the enhancement of the awareness of safety and environmental protection of people. The water-based polyurethane adhesive is formed by dissolving or dispersing polyurethane in water, and has the advantages of no solvent, no pollution, good film forming property, strong bonding force, easy mixing with other polymers, particularly emulsion polymers, and the like, compared with a solvent type adhesive. After 90 s, the adhesive has been gradually applied to the aspects of automobile inner decoration, kitchen article manufacturing, composite film manufacturing, sole and upper adhesion, garment processing and the like. However, there are many disadvantages that the functions thereof need to be perfected by various modifications.
In addition to maintaining the advantages of polyurethane, aqueous polyurethane adhesives are unique compared to solvent-based polyurethane adhesives.
The water is used as a medium, is non-toxic and non-inflammable, is pollution-free, non-dangerous, small in smell, free of environmental pollution, energy-saving and suitable for substrates easily corroded by organic solvents.
The viscosity is low, the water-soluble thickening agent and water can be used for adjusting, the operation is convenient, and the residual glue is easy to clean.
Can be mixed with various aqueous resins to improve performance and reduce cost, but care should be taken with respect to ionic properties and acid-base properties to prevent agglomeration.
Contains carboxyl, hydroxyl and other groups, and can participate in reaction under proper conditions to generate crosslinking and improve performance.
After retrieval, for example, chinese patent literature discloses a preparation method of a sulfonic acid type aqueous polyurethane adhesive [ application No.: CN 201310151655.4; publication No.: CN103254867A ]. The preparation method comprises the following steps of preparing raw materials of the sulfonic acid type waterborne polyurethane adhesive from polyol, diisocyanate, a cross-linking agent, a sulfonate hydrophilic chain extender and a diamine chain extender, wherein the catalyst is an organic tin catalyst, and the use amount of each component is expressed by weight percentage as follows: 75-89% of polyol, 8.5-22% of diisocyanate, 0.06-0.10% of cross-linking agent, 1.0-3.0% of sulfonate hydrophilic chain extender, 0.08-0.15% of diamine chain extender and 0.02-0.05% of organic tin catalyst, wherein the polyol is polyester polyol or polyether polyol or a mixture of the polyester polyol and the polyether polyol, and the sulfonate hydrophilic chain extender is ethylenediamine ethanesulfonic acid sodium or 1, 2-dihydroxy-3-propanesulfonic acid sodium.
Although the prepared sulfonic acid type waterborne polyurethane adhesive has the characteristics of high solid content, low minimum activation temperature and high peeling strength, the production efficiency is low and the energy consumption is high.
Based on the above, the preparation method of the waterborne polyurethane adhesive is provided, and the preparation method adopts a multistage stirring device for mixing production, so that the production time is short, and the efficiency is high; the unit power consumption is low; the invention has scientific and reasonable raw material matching, good bonding effect, stable process and better market prospect;
the multistage stirring device has a compact structure, occupies a small area, realizes the simultaneous production of A, B parts, uniformly discharges materials, quickly stirs the materials, and has high efficiency and low energy consumption; the constant temperature stirring is guaranteed in the cooperation of heating stirred tank and control heater and a heat preservation section of thick bamboo, and the agitator tank that adjusts the temperature and a heat preservation section of thick bamboo cooperation carry out effective rapid cooling to its agitator tank inside material that adjusts the temperature, guarantee the misce bene, and the stirring misce bene improves compounding efficiency, and the while is inside the proportional injection mixing agitator tank, carries out quick high strength stirring, and production efficiency is high.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a preparation method of a water-based polyurethane adhesive, and aims to solve the technical problems that: how to realize efficient production preparation, stable process, multistage type agitating unit compact structure simultaneously, area occupied is little, realizes A, B two parts simultaneous production, even blanking, rapid mixing, efficient, the energy consumption is low.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the water-based polyurethane adhesive comprises the following steps of: (8.5-9.5) and mixing the part A and the part B, wherein the part A is prepared from the following raw materials in parts by weight: 110-115 parts of aromatic diisocyanate, 180-200 parts of polyether polyol, 150-170 parts of poly adipic acid-1, 4-butanediol diol, 29-34 parts of dimethylolpropionic acid, 14-19 parts of a salt forming agent, 0.6-2.5 parts of a chain extender and 66-69 parts of an organic solvent; the part B is prepared from the following raw materials in parts by weight: 16.5-17.5 parts of aromatic diisocyanate, 16.5-17.5 parts of isophorone diisocyanate, 11-14 parts of polyether glycol I, 11-14 parts of polyether glycol II, 21-24 parts of polyether glycol III, 13-15 parts of polyether glycol IV, 2.5-4.5 parts of diethylene glycol and 31-39 parts of ethyl acetate (the same weight parts are used).
The method comprises the following steps:
step one, weighing aromatic diisocyanate, polyether polyol I and poly adipic acid-1, 4-butanediol glycol ester diol, adding into a stirring device after weighing, starting stirring, introducing nitrogen for protection, heating to 40 +/-1 ℃, adding a catalyst, gradually heating to 70 +/-1 ℃, stirring for reaction for 1 +/-0.1 h, adding dimethylolpropionic acid, gradually heating to 80 +/-1 ℃, reacting for 2 +/-0.1 h, then gradually heating to 90 +/-1 ℃, reacting for 3 +/-0.5 h to make NCO mass fraction reach 2.6-2.7%, and adding an organic solvent to prepare a prepolymer;
Step two, calculating the using amount of a chain extender and a salt former according to the mass fraction of NCO and the using amount of dimethylolpropionic acid, adding the chain extender and the salt former into deionized water for dispersion in advance, and then adding a prepolymer for full stirring and dispersion to prepare a part A;
step three, weighing the polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol, adding the weighed polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol into stirring equipment, heating the mixture to 70 +/-2 ℃, stirring the mixture for reaction for 1 +/-0.1 h, adding the polyether polyol IV, further reacting the mixture for 4 +/-0.5 h, measuring the mass fraction of NCO, adding ethyl acetate when the mass fraction reaches a theoretical value (7 +/-0.1%), continuing stirring, cooling and discharging the mixture to obtain a part B;
taking the part A and the part B in parts by weight as 100: (8.5-9.5), adding a certain amount of additives such as drying agents, flame retardants, coupling agents, antioxidants, ultraviolet inhibitors, coloring agents, adhesion promoters, fillers or plasticizers according to needs, placing the mixture into stirring equipment for stirring for 4 +/-1 min to obtain the waterborne polyurethane adhesive.
The part A is semitransparent milky white liquid, the solid content is 28 +/-0.5%, the viscosity is 13 +/-3 mPa & s at 25 ℃, the pH value is 7 +/-0.2, and the density is 1 +/-0.05 g/m.
The part B is colorless transparent viscous liquid, the solid content is 90 +/-0.5%, the viscosity is 11 +/-1 mPa & s at 25 ℃, and the density is 1.15 +/-0.05 g/mL.
The water-based polyurethane adhesive is milky white, has the solid content of 33 +/-4 percent, the viscosity of 25 +/-5 mPa & s at 25 ℃, the density of 1.06 +/-0.01 g/mL and the pot life of 12 +/-0.5 h.
The dimethylolpropionic acid is ground and crushed by a grinding mechanism, the fineness of the dimethylolpropionic acid is more than or equal to 80 meshes, and the molar ratio of the salt forming agent to the dimethylolpropionic acid is (0.73-0.78): 1.
the organic solvent is one of acetone, methyl ethyl ketone or N, N-dimethylformamide; the chain extender adopts one of 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, ethylenediamine, N-dihydroxy or aniline; the salt forming agent is one of triethylamine, methylamine, ethanolamine or dimethylethanolamine; the aromatic diisocyanate adopts one of toluene diisocyanate, diphenylmethane diisocyanate or 1, 5-naphthalene diisocyanate; the polyether polyol I, the polyether polyol II, the polyether polyol III and the polyether polyol IV respectively adopt one of polyoxypropylene diol, polytetrahydrofuran diol, polyoxytetramethylene diol, polyethylene glycol or polytetramethylene glycol; the catalyst in the first step adopts stannous octoate, lead octoate or dibutyltin dilaurate; and the pH value of the deionized water in the second step is 7 +/-0.1.
The moisture content of each component of the part B is less than 0.1 percent.
The stirring equipment used in the first step to the fourth step is a multi-stage stirring device, the multi-stage stirring device comprises a mounting frame, a mixing stirring tank, two heat preservation cylinders II, two heat preservation cylinders I and a plurality of grinding mechanisms are sequentially arranged on the mounting frame from bottom to top, temperature-adjusting stirring tanks are arranged in the heat preservation cylinders II, heating stirring kettles are arranged in the heat preservation cylinders I, heaters are arranged on the heat preservation cylinders I, the heaters are connected with the heat preservation cylinders I through pipelines, the heating stirring kettles on the same sides of the grinding mechanisms are connected through flexible pipelines, the heating stirring kettles are connected with the temperature-adjusting stirring tanks on the same sides through pipelines, and the temperature-adjusting stirring tanks are connected with the mixing stirring tanks;
the grinding mechanism is matched with a discharge port of corresponding discharging equipment for discharging, the fineness of particles is adjusted according to the mixing requirement of raw materials, the ground materials fall into the heating stirring kettle after being ground by the grinding mechanism, adding other materials, stirring, controlling the heater to heat the first heat-insulating cylinder to control the stirring temperature of the heating and stirring kettle, stirring to obtain prepolymer, adding the prepolymer into the same-side temperature-regulating stirring tank, adding other related materials, stirring to obtain part A at room temperature, proportionally adding into the mixing and stirring tank, and simultaneously, heating the other side of the stirring kettle, stirring to prepare a hot part B, injecting the hot part B into the same-side temperature-regulating stirring tank, stirring to prepare a room-temperature part B, injecting the part B into a mixing and stirring tank in proportion, and performing high-rotation-speed strong stirring in the mixing and stirring tank to form the waterborne polyurethane adhesive.
The mounting frame comprises a base frame, a plurality of uniformly distributed support legs are arranged at the lower end of the base frame, a vertical frame and a plurality of circumferentially uniformly distributed protective guards are arranged on the upper side of the base frame, a second mounting plate is arranged on the front side of the vertical frame, two mounting holes are formed in the second mounting plate, a first mounting plate is arranged at the upper end of the vertical frame, a walking frame is arranged at the upper end of the first mounting plate, and a crawling ladder is arranged between the first mounting plate and the vertical frame;
the mixing and stirring tank is fixed above the base frame, two feeding main pipes are arranged at the upper end of the mixing and stirring tank, the feeding main pipes are respectively positioned below the corresponding temperature-regulating stirring tanks, and discharge valves are arranged below the mixing and stirring tanks; and (4) carrying out high-speed strong stirring in the mixing and stirring tank to form the waterborne polyurethane adhesive, and discharging the waterborne polyurethane adhesive through a discharge valve.
The second heat-insulation cylinder is positioned in the mounting hole, a plurality of mounting lugs which are uniformly distributed on the circumference are arranged on the outer side of the second heat-insulation cylinder, the mounting lugs are fixed on a second mounting plate, two connecting pipes are arranged on the second heat-insulation cylinder, one of the connecting pipes is connected with an external water source, a plurality of feeding pipes are arranged at the upper end of the temperature-adjusting stirring tank, one of the feeding pipes is connected with the external water source, a second three-way pipe is arranged at the lower end of the temperature-adjusting stirring tank, second electric control valves are arranged at the other two ends of the second three-way pipe, one of the second electric control valves is connected with the feeding main pipe at the same side through a pipeline, and the other second electric control valve is connected with a drain pipe; the inside stirring of agitator tank that adjusts the temperature forms the material, discharge via the automatically controlled valve of second, through the pipeline, the feeding that gets into the homonymy is responsible for, pour into the mixing agitator tank inside, outside water source is connected to one of them inlet pipe, after the reaction is accomplished, the water injection is washd, the abluent sewage is discharged through the blow off pipe that the automatically controlled valve of another second is connected, outside water source is connected to one of them connecting pipe, cool down to the agitator tank that adjusts the temperature, carry out effective rapid cooling to its agitator tank inside material that adjusts the temperature.
The first heat-insulation barrel is fixed on a first mounting plate, a first temperature sensor and a second temperature sensor are arranged on the first mounting plate, the first temperature sensor extends into a heating and stirring kettle, a kettle cover is detachably arranged on the heating and stirring kettle, a plurality of feeding connecting pipes are arranged on the kettle cover, one of the feeding connecting pipes is connected with an external water source, one of the feeding connecting pipes is connected with external hot air, a protective cover is arranged on the kettle cover, the lower end of the protective cover is hinged to the heating and stirring kettle, a stirring motor is arranged on the protective cover, a first stirring frame is rotatably arranged on the kettle cover and located inside the heating and stirring kettle, a chain wheel pair is arranged between the first stirring frame and the stirring motor and located on the inner side of the protective cover, and an electric push rod is hinged between the first heat-insulation barrel and the protective cover;
temperature sensor two detects the inside temperature of a heat preservation section of thick bamboo, temperature sensor one detects the inside temperature of heating stirred tank, electric putter is collapsible, it is closed or open to drive the kettle cover, agitator motor passes through the vice first stirring frame of drive of sprocket and rotates, carry out the stirring of material, outside water source is connected to one of them feeding connecting pipe, after the reaction is accomplished, the water injection is washd, after the washing is accomplished, outside steam is connected to one of them feeding connecting pipe, dry to inside, guarantee inside dry.
The first heat-preserving cylinder is provided with an installation bracket, the heater is fixed on the installation bracket, a heat inlet pipe is connected between the liquid discharge end of the heater and the first heat-preserving cylinder, and a heat outlet pipe is also arranged on the first heat-preserving cylinder;
and adding external cold water into the heater, heating to generate hot water, allowing the hot water to pass through a liquid discharge end of the heater, enter the first heat-preserving cylinder through the heat pipe, and discharging redundant cold water from the heat discharge pipe.
A first three-way pipe is arranged at the lower end of the heating stirring kettle, first electric control valves are arranged at the other two ends of the first three-way pipe, one of the first electric control valves is connected with a feed pipe at the upper end of the temperature-adjusting stirring tank at the same side through a pipeline, and the other first electric control valve is connected with a drain pipe;
stirring motor passes through the first stirring frame of sprocket pair drive and rotates, carries out the stirring of material, and the back is accomplished in the stirring, through one of them first automatically controlled valve, via pipeline, the inside of inlet pipe injection homonymy's the agitator tank that adjusts the temperature, abluent sewage passes through the blow off pipe via another one first automatically controlled valve and discharges.
The grinding mechanism comprises a limiting seat, the limiting seat is sleeved on the walking frame and abutted against the lower side of the walking frame, two symmetrical limiting wheels are arranged inside the limiting seat and abutted against the two sides of the walking frame respectively, a storage barrel is arranged at the upper end of the limiting seat, a walking wheel is rotatably arranged inside the storage barrel and abutted against the groove of the walking frame, a walking motor is fixed outside the storage barrel, an output shaft of the walking motor is in transmission connection with the walking wheel, a grinding barrel is fixed at the upper end of the storage barrel, a grinding motor is fixed below the grinding barrel, a grinding movable disk is fixed on the output shaft of the grinding motor, an adjusting screw disc is screwed at the upper end of the grinding barrel, a locking screw is screwed on the grinding barrel, the end part of the locking screw is abutted against the adjusting screw disc, a grinding fixed disc is arranged at the lower end of the adjusting screw disc, a feeding hopper is arranged at the upper end of the adjusting screw disc, a control gauge plate is arranged between the feeding hopper and the adjusting screw disc, a discharge valve is arranged on the side part of the grinding cylinder, and a flexible pipeline is connected between the discharge valve and the feeding connecting pipe;
The walking motor drives the walking wheels to rotate, the walking wheels are matched with the limiting wheels and the limiting base to walk along the walking frame, thereby driving the feed hopper to move, being convenient to be matched with a discharge port of corresponding discharging equipment for discharging, according to the mixing requirement of raw materials, namely, the contact area between the solid powder and the liquid reactant is increased, the finer the particle size is, the faster the reaction speed is, the adjusting screw disc is rotated to adjust the distance between the grinding fixed disc and the grinding movable disc, adjust the particle fineness promptly, then screw up locking screw, locking screw's tip is contradicted on adjusting the spiral shell dish, locks this and grinds the granularity, inside the feeder hopper was arrived to the blowing equipment blowing, and the flow can be adjusted to the accuse volume board, and grinding motor drives and grinds the movable disk and rotate, grinds the fixed disk and grinds the movable disk cooperation, forms the powder, opens the bleeder valve, and the blowing passes through flexible pipeline and gets into inside the feeding connecting tube.
Compared with the prior art, the preparation method of the waterborne polyurethane adhesive has the following advantages:
the preparation method adopts a multistage stirring device for mixed production, and has short production time and high efficiency; the unit power consumption is low; the invention has scientific and reasonable raw material collocation, good bonding effect, stable process and better market prospect;
The multistage stirring device has a compact structure, occupies a small area, realizes the simultaneous production of A, B parts, uniformly discharges materials, quickly stirs the materials, and has high efficiency and low energy consumption; the constant temperature stirring is guaranteed in the cooperation of heating stirred tank and control heater and a heat preservation section of thick bamboo, and the agitator tank that adjusts the temperature and a heat preservation section of thick bamboo cooperation carry out effective rapid cooling to its agitator tank inside material that adjusts the temperature, guarantee the misce bene, and the stirring misce bene improves compounding efficiency, and the while is inside the proportional injection mixing agitator tank, carries out quick high strength stirring, and production efficiency is high.
Drawings
FIG. 1 is a flow chart of a method for preparing an aqueous polyurethane adhesive according to the present invention.
FIG. 2 is a diagram showing the formulation of the aqueous polyurethane adhesive according to the present invention.
FIG. 3 is a schematic front side perspective view of the multistage stirring apparatus of the present invention.
FIG. 4 is a schematic rear side perspective view of the multistage stirring apparatus of the present invention.
FIG. 5 is a perspective view of a mounting frame of the multistage stirring apparatus of the present invention.
FIG. 6 is a schematic view of the rear side of a heated stirred tank of the multistage stirring apparatus of the present invention.
FIG. 7 is a schematic front side perspective view of a heated stirred tank of the multistage stirring apparatus of the present invention.
FIG. 8 is a schematic perspective view of a grinding mechanism of the multistage stirring apparatus of the present invention.
FIG. 9 is a schematic sectional view showing the structure of the polishing mechanism of the multistage stirring apparatus of the present invention.
In the figure, 1, a mounting frame; 2. a mixing and stirring tank; 3. a temperature-adjusting stirring tank; 4. heating the stirred tank; 5. a grinding mechanism; 6. a first heat-preserving cylinder; 7. a heater; 8. a first three-way pipe; 9. a first electrically controlled valve; 10. a second heat-preservation cylinder; 11. mounting ears; 12. a second three-way pipe; 13. a second electrically controlled valve; 14. a feed main pipe; 15. a discharge valve; 16. a base frame; 17. protecting the fence; 18. a second mounting plate; 19. a first mounting plate; 20. a walking frame; 21. climbing a ladder; 22. a feeding connecting pipe; 23. a protective cover; 24. a stirring motor; 25. mounting a bracket; 26. an electric push rod; 27. a first temperature sensor; 28. a second temperature sensor; 29. a heat inlet pipe; 30. discharging the heat pipe; 31. a feed hopper; 32. a quantity control plate; 33. adjusting a screw disc; 34. locking the screw rod; 35. a grinding cylinder; 36. a traveling motor; 37. a storage barrel; 38. a limiting seat; 39. a discharge valve; 40. grinding the fixed disc; 41. grinding the movable disc; 42. grinding the motor; 43. a traveling wheel; 44. a limiting wheel.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
As shown in fig. 1-2, the preparation method of the waterborne polyurethane adhesive comprises the following steps: (8.5-9.5) and part B, wherein the part A is prepared by mixing the following raw materials in parts by weight: 110-115 parts of aromatic diisocyanate, 180-200 parts of polyether polyol, 150-170 parts of poly (1, 4-butanediol adipate) glycol, 29-34 parts of dimethylolpropionic acid, 14-19 parts of a salt forming agent, 0.6-2.5 parts of a chain extender and 66-69 parts of an organic solvent; the part B is prepared from the following raw materials in parts by weight: 16.5-17.5 parts of aromatic diisocyanate, 16.5-17.5 parts of isophorone diisocyanate, 11-14 parts of polyether glycol I, 11-14 parts of polyether glycol II, 21-24 parts of polyether glycol III, 13-15 parts of polyether glycol IV, 2.5-4.5 parts of diethylene glycol and 31-39 parts of ethyl acetate (the same weight parts are used).
The method comprises the following steps:
step one, weighing aromatic diisocyanate, polyether polyol I and poly adipic acid-1, 4-butanediol ester diol, adding the weighed components into a stirring device, starting stirring, introducing nitrogen for protection, heating to 40 +/-1 ℃, adding a catalyst, gradually heating to 70 +/-1 ℃, stirring for reaction for 1 +/-0.1 hour, adding dimethylolpropionic acid, gradually heating to 80 +/-1 ℃, reacting for 2 +/-0.1 hour, then gradually heating to 90 +/-1 ℃, reacting for 3 +/-0.5 hour to enable the NCO mass fraction to reach 2.6-2.7%, and adding an organic solvent to prepare a prepolymer;
Calculating the use amounts of a chain extender and a salt forming agent according to the mass fraction of NCO and the use amount of dimethylolpropionic acid, adding the chain extender and the salt forming agent into deionized water for dispersion in advance, adding a prepolymer, and fully stirring and dispersing to obtain a part A;
step three, weighing the polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol, adding the weighed polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol into stirring equipment, heating the mixture to 70 +/-2 ℃, stirring the mixture for reaction for 1 +/-0.1 h, adding the polyether polyol IV, further reacting the mixture for 4 +/-0.5 h, measuring the mass fraction of NCO, adding ethyl acetate when the mass fraction reaches a theoretical value (7 +/-0.1%), continuing stirring, cooling and discharging the mixture to obtain a part B;
step four, taking the part A and the part B in parts by weight as 100: (8.5-9.5), adding a certain amount of additives such as drying agents, flame retardants, coupling agents, antioxidants, ultraviolet inhibitors, coloring agents, adhesion promoters, fillers or plasticizers according to needs, placing the mixture into a stirring device for stirring for 4 +/-1 min to obtain the waterborne polyurethane adhesive.
Part A is semitransparent milky white liquid with a solid content of 28 +/-0.5 percent, a viscosity of 13 +/-3 mPa & s at 25 ℃, a pH value of 7 +/-0.2 and a density of 1 +/-0.05 g/mL.
The part B is colorless transparent viscous liquid, the solid content is 90 +/-0.5%, the viscosity at 25 ℃ is 11 +/-1 mPa & s, and the density is 1.15 +/-0.05 g/mL.
The waterborne polyurethane adhesive is milky white, has the solid content of 33 +/-4 percent, the viscosity of 25 +/-5 mPa & s at 25 ℃, the density of 1.06 +/-0.01 g/mL and the working life of 12 +/-0.5 h.
The dimethylolpropionic acid is ground and crushed by a grinding mechanism, the fineness of the dimethylolpropionic acid is more than or equal to 80 meshes, and the molar ratio of the salt forming agent to the dimethylolpropionic acid is (0.73-0.78): 1.
the organic solvent is one of acetone, methyl ethyl ketone or N, N-dimethylformamide; the chain extender adopts one of 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, ethylenediamine, N-dihydroxy or aniline; the salt forming agent is one of triethylamine, methylamine, ethanolamine or dimethylethanolamine; the aromatic diisocyanate is one of toluene diisocyanate, diphenylmethane diisocyanate or 1, 5-naphthalene diisocyanate; the polyether glycol I, the polyether glycol II, the polyether glycol III and the polyether glycol IV are respectively one of polyoxypropylene glycol, polytetrahydrofuran glycol, polyoxytetramethylene glycol, polyethylene glycol or polytetramethylene glycol; the catalyst in the first step adopts stannous octoate, lead octoate or dibutyltin dilaurate; and the pH value of the deionized water in the second step is 7 +/-0.1.
The moisture content of the components of part B is less than 0.1%.
As shown in fig. 3-9, the stirring apparatus used in the first step to the fourth step is a multistage stirring apparatus, the multistage stirring apparatus includes a mounting rack 1, a mixing stirring tank 2, two heat-insulating cylinders two 10, two heat-insulating cylinders one 6 and a plurality of grinding mechanisms 5 are sequentially arranged on the mounting rack 1 from bottom to top, the temperature-adjusting stirring tank 3 is arranged inside each heat-insulating cylinder two 10, each heat-insulating cylinder one 6 is provided with a heating stirring tank 4, each heat-insulating cylinder one 6 is provided with a heater 7, the heaters 7 are connected with the heat-insulating cylinders one 6 through pipelines, the heating stirring tanks 4 on the same sides of the grinding mechanisms 5 are connected through flexible pipelines, the heating stirring tanks 4 are connected with the temperature-adjusting stirring tanks 3 on the same sides through pipelines, and the temperature-adjusting stirring tanks 3 are connected with the mixing stirring tank 2.
By adopting the structure, the grinding mechanism 5 is matched with a discharge port of corresponding discharging equipment for discharging, the particle fineness is adjusted according to the mixing requirement of raw materials, the ground grinding mechanism 5 falls into the heating stirring kettle 4 to be stirred after being ground, the other materials are added, the heater 7 is controlled to heat the first heat-insulating cylinder 6, the stirring temperature of the heating stirring kettle 4 is controlled, a prepolymer is prepared after the stirring of the stirring kettle 4 at one side is completed, the prepolymer is injected into the temperature-adjusting stirring tank 3 at the same side, the other related materials are added to be stirred to prepare the part A at room temperature, the part A is injected into the mixing stirring tank 2 in proportion, the part B which is heated after the stirring of the stirring kettle 4 at the other side is completed is injected into the temperature-adjusting stirring tank 3 at the same side, the part B at room temperature is prepared by stirring, the part B is injected into the mixing stirring tank 2 in proportion, and the mixing stirring tank 2 is used for high-speed strong stirring, forming the water-based polyurethane adhesive.
The mounting frame 1 comprises a base frame 16, a plurality of uniformly distributed support legs are arranged at the lower end of the base frame 16, a vertical frame and a plurality of circumferentially and uniformly distributed protective guards 17 are arranged on the upper side of the base frame 16, a second mounting plate 18 is arranged on the front side of the vertical frame, two mounting holes are formed in the second mounting plate 18, a first mounting plate 19 is arranged at the upper end of the vertical frame, a walking frame 20 is arranged at the upper end of the first mounting plate 19, and a ladder 21 is arranged between the first mounting plate 19 and the vertical frame;
the mixing and stirring tank 2 is fixed above the base frame 16, two feeding main pipes 14 are arranged at the upper end of the mixing and stirring tank 2, the feeding main pipes 14 are respectively positioned below the corresponding temperature-regulating stirring tanks 3, and discharge valves 15 are arranged below the mixing and stirring tank 2; the mixing and stirring tank 2 is intensively stirred at a high rotating speed to form the waterborne polyurethane adhesive, and the waterborne polyurethane adhesive is discharged through a discharge valve 15.
The second heat-insulating cylinder 10 is positioned in the mounting hole, a plurality of mounting lugs 11 which are uniformly distributed on the circumference are arranged on the outer side of the second heat-insulating cylinder 10, the mounting lugs 11 are fixed on a second mounting plate 18, two connecting pipes are arranged on the second heat-insulating cylinder 10, one of the connecting pipes is connected with an external water source, a plurality of feeding pipes are arranged at the upper end of the temperature-adjusting stirring tank 3, one of the feeding pipes is connected with the external water source, a second three-way pipe 12 is arranged at the lower end of the temperature-adjusting stirring tank 3, second electric control valves 13 are arranged at the other two ends of the second three-way pipe 12, one of the second electric control valves 13 is connected with a feeding main pipe 14 at the same side through a pipeline, and the other second electric control valve 13 is connected with a sewage discharge pipe; the inside stirring of agitator tank 3 that adjusts the temperature forms the material, discharge via second automatically controlled valve 13, through the pipeline, the feeding that gets into the homonymy is responsible for 14, pour into 2 insides of mixing agitator tank, outside water source is connected to one of them inlet pipe, after the reaction is accomplished, the water injection is washd, abluent sewage is discharged through the blow off pipe that another second automatically controlled valve 13 is connected, outside water source is connected to one of them connecting pipe, cool down to agitator tank 3 that adjusts the temperature, carry out effective rapid cooling to its agitator tank 3 inside material that adjusts the temperature.
The first heat-preserving cylinder 6 is fixed on the first mounting plate 19, a first temperature sensor 27 and a second temperature sensor 28 are arranged on the first mounting plate 18, the first temperature sensor 27 extends into the heating and stirring kettle 4, a kettle cover is detachably arranged on the heating and stirring kettle 4, a plurality of feeding connecting pipes 22 are arranged on the kettle cover, one of the feeding connecting pipes 22 is connected with an external water source, one of the feeding connecting pipes 22 is connected with external hot air, a protective cover 23 is arranged on the kettle cover, the lower end of the protective cover 23 is hinged to the heating and stirring kettle 4, a stirring motor 24 is arranged on the protective cover 23, a first stirring frame is rotatably arranged on the kettle cover and located inside the heating and stirring kettle 4, a chain wheel pair is arranged between the first stirring frame and the stirring motor 24 and located on the inner side of the protective cover 23, and an electric push rod 26 is hinged between the first heat-preserving cylinder 6 and the protective cover 23;
two 28 temperature that detect a heat preservation section of thick bamboo 6 inside of temperature sensor, a 27 temperature that detect heating stirred tank 4 inside of temperature sensor, electric putter 26 is collapsible, it is closed or open to drive the kettle cover, agitator motor 24 passes through the vice first stirring frame of drive of sprocket and rotates, carry out the stirring of material, outside water source is connected to one of them feeding connecting pipe 22, after the reaction is accomplished, the water injection is washd, after the washing is accomplished, outside steam is connected to one of them feeding connecting pipe 22, dry to inside, guarantee inside drying.
A mounting bracket 25 is arranged on the first heat-preservation cylinder 6, the heater 7 is fixed on the mounting bracket 25, a heat inlet pipe 29 is connected between the liquid discharge end of the heater 7 and the first heat-preservation cylinder 6, and a heat outlet pipe 30 is also arranged on the first heat-preservation cylinder 6;
and external cold water is added into the heater 7 and heated to generate hot water, the hot water passes through the liquid discharge end of the heater 7 and enters the first heat preservation cylinder 6 through the heat pipe 29, and redundant cold water is discharged from the heat discharge pipe 30.
A first three-way pipe 8 is arranged at the lower end of the heating and stirring kettle 4, first electric control valves 9 are arranged at the other two ends of the first three-way pipe 8, one first electric control valve 9 is connected with a feed pipe at the upper end of the temperature-adjusting stirring tank 3 at the same side through a pipeline, and the other first electric control valve 9 is connected with a blow-off pipe;
stirring motor 24 passes through the vice first stirring frame rotation of drive of sprocket, carries out the stirring of material, and the back is accomplished in the stirring, through one of them first automatically controlled valve 9, via pipeline, inlet pipe injection homonymy the agitator tank 3 that adjusts the temperature inside, abluent sewage passes through the blow off pipe via another one first automatically controlled valve 9 and discharges.
The grinding mechanism 5 comprises a limiting seat 38, the limiting seat 38 is sleeved on the walking frame 20, the limiting seat 38 abuts against the lower side of the walking frame 20, two symmetrical limiting wheels 44 are arranged inside the limiting seat 38, the limiting wheels 44 respectively abut against two sides of the walking frame 20, an object placing barrel 37 is arranged at the upper end of the limiting seat 38, a walking wheel 43 is rotatably arranged inside the object placing barrel 37, the walking wheel 43 abuts against the groove of the walking frame 20, a walking motor 36 is fixed outside the object placing barrel 37, an output shaft of the walking motor 36 is in transmission connection with the walking wheel 43, a grinding barrel 35 is fixed at the upper end of the object placing barrel 37, a grinding motor 42 is fixed below the grinding barrel 35, a grinding movable disk 41 is fixed on an output shaft of the grinding motor 42, an adjusting screw disk 33 is screwed at the upper end of the grinding barrel 35, a locking screw 34 is screwed on the grinding barrel 35, the end of the locking screw 34 is on the adjusting screw disk 33, a grinding fixed disk 40 is arranged at the lower end of the adjusting screw disk 33, the upper end of the adjusting screw disk 33 is provided with a feed hopper 31, a quantity control plate 32 is arranged between the feed hopper 31 and the adjusting screw disk 33, the side part of the grinding cylinder 35 is provided with a discharge valve 39, and a flexible pipeline is connected between the discharge valve 39 and the feeding connecting pipe 22.
The walking motor 36 drives the walking wheel 43 to rotate, the walking wheel 43 cooperates with the limiting wheel 44 and the limiting base 38 to walk along the walking frame 20, thereby driving the feeding hopper 31 to move, and conveniently cooperates with the discharge port of the corresponding discharging device for discharging, the contact area between the solid powder and the liquid reactant is increased according to the mixing requirement of the raw materials, the smaller the particle diameter is, the faster the reaction speed is, the regulating screw disc 33 is rotated to regulate the distance between the grinding fixed disc 40 and the grinding movable disc 41, i.e. the particle fineness is regulated, then the locking screw 34 is screwed, the end part of the locking screw 34 abuts against the regulating screw disc 33 to lock the grinding particle fineness, the discharging device discharges the raw materials into the feeding hopper 31, the flow rate can be regulated by the flow control plate 32, the grinding motor 42 drives the grinding movable disc 41 to rotate, the grinding fixed disc 40 cooperates with the grinding movable disc 41 to grind, a product is formed, the discharging valve 39 is opened, the discharge is passed through a flexible tube into the interior of the feed connector tube 22.
Example 1
A waterborne polyurethane adhesive is prepared from the following components in parts by weight of 100: 9, mixing the part A and the part B, wherein the part A is prepared from the following raw materials in parts by weight: 115 parts of aromatic diisocyanate, 200 parts of polyether polyol, 170 parts of poly (1, 4-butanediol adipate) diol, 34 parts of dimethylolpropionic acid, 19 parts of salt forming agent, 2.5 parts of chain extender and 69 parts of organic solvent (the weight of each part is the same);
The part B is prepared from the following raw materials in parts by weight: 17.5 parts of aromatic diisocyanate, 17.5 parts of isophorone diisocyanate, 14 parts of polyether polyol, 24 parts of polyether polyol, 15 parts of polyether polyol, 4.5 parts of diethylene glycol and 39 parts of ethyl acetate (the weight of each part is the same);
step one, after weighing aromatic diisocyanate, polyether polyol I and poly adipic acid-1, 4-butanediol ester diol, guiding the aromatic diisocyanate, the polyether polyol I and the poly adipic acid-1, 4-butanediol ester diol into a heating and stirring kettle 4 at one side through a plurality of feeding connecting pipes 22, starting stirring, driving a first stirring frame to rotate through a chain wheel pair by a stirring motor 24, stirring materials, injecting nitrogen for protection through the feeding connecting pipes 22, matching with a first heat-insulating cylinder 6 through a heater 7, heating to 40 ℃, adding a catalyst through the feeding connecting pipes 22, gradually heating to 70 ℃, after stirring reaction for 1h, driving a walking wheel 43 to rotate by a walking motor 36, matching the walking wheel 43 with a limiting wheel 44 and a limiting seat 38, walking along a walking frame 20, driving a feeding hopper 31 to move, conveniently matching with a discharge port of corresponding discharging equipment for discharging, and increasing the contact area of solid powder and liquid reactants according to the mixing requirements of the raw materials, the finer the particle size, the faster the reaction speed, the rotating adjusting screw 33, adjusting the distance between the fixed grinding disc 40 and the movable grinding disc 41, i.e. adjusting the particle fineness, then screwing the locking screw 34, the end of the locking screw 34 abutting against the adjusting screw 33, locking the particle size of the ground particles, introducing dimethylolpropionic acid into the hopper 31 by the discharge equipment, the flow rate of which can be adjusted by the control plate 32, the grinding motor 42 driving the movable grinding disc 41 to rotate, the fixed grinding disc 40 matching with the movable grinding disc 41, grinding to form powder, opening the discharge valve 39, discharging through the flexible pipe and the feed connection pipe 22, into the heating and stirring vessel 4, gradually increasing the temperature to 80 ℃, reacting for 2h, gradually increasing the temperature to 90 +/-1 ℃, reacting for 3h to make the NCO mass fraction reach 2.6% -2.7%, adding an organic solvent through the feed connection pipe 22, stirring to obtain a prepolymer, the total time is 6h, and the mixture is injected into the temperature-adjusting stirring tank 3 at the same side through a pipeline and a feed pipe by one of the first electric control valves 9;
Secondly, calculating the use amounts of a chain extender and a salt forming agent according to the mass fraction of NCO and the use amount of dimethylolpropionic acid, injecting the chain extender and the salt forming agent into the temperature-adjusting stirring tank 3 at the same side through a feed pipe, adding dispersed deionized water into the temperature-adjusting stirring tank 3 in advance, connecting one connecting pipe with an external water source, cooling the temperature-adjusting stirring tank 3, effectively and quickly cooling the materials in the temperature-adjusting stirring tank 3, fully stirring and dispersing for 1h to prepare a part A at room temperature, and injecting the part A into the mixing stirring tank 2 through a main feed pipe 14 at one side according to a proportion;
step three, simultaneously, weighing the polyether glycol I, the polyether glycol II, the polyether glycol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol, guiding the weighed materials into the heating stirring kettle 4 at the other side through a plurality of feeding connecting pipes 22, starting stirring, driving a first stirring frame to rotate through a chain wheel pair by a stirring motor 24, stirring the materials, matching the materials with a heat preservation cylinder I6 through a heater 7, heating the materials to 70 ℃, adding the polyether glycol IV through the feeding connecting pipes 22 after stirring and reacting for 1h, measuring the mass fraction of NCO after further reacting for 4h, adding ethyl acetate through the feeding connecting pipes 22 when the mass fraction of NCO reaches a theoretical value (7 +/-0.1 percent), continuously stirring for 1h to prepare a hot part B, injecting the hot part B into the temperature-adjusting stirring tank 3 at the same side through a pipeline and a feeding pipe through one of the first electric control valves 9, one connecting pipe is connected with an external water source, the temperature regulating stirring tank 3 is cooled, the materials in the temperature regulating stirring tank 3 are effectively and quickly cooled, the stirring is continued, the stirring is carried out to obtain a part B of the room temperature, and the part B is proportionally injected into the mixing and stirring tank 2 through the feeding main pipe 14 on the other side for 6 hours;
Step four, according to the weight part ratio of the part A to the part B of 100: 9, according to the mixing requirement, calculating to obtain the volume ratio of the part A to the part B of 12:1, wherein the specifications of the first electric control valve 9 and the second electric control valve 13 are the same, so that the opening time ratio of the first electric control valve 9 to the second electric control valve 13 is 12:1, injecting the mixture into the mixing and stirring tank 2, adding a certain amount of additives such as a drying agent, a flame retardant, a coupling agent, an antioxidant, an ultraviolet inhibitor, a coloring agent, an adhesion promoter, a filler or a plasticizer according to the requirement, placing the mixture into stirring equipment for stirring at the rotating speed of 2000r/min for 4 +/-1 min to obtain the waterborne polyurethane adhesive;
after the use is finished, one of the feeding pipes can be connected with an external water source, after the reaction is finished, water is injected for cleaning, the cleaned sewage is discharged through a sewage discharge pipe connected with the other second electric control valve 13, one of the feeding connecting pipes 22 is connected with the external water source, after the reaction is finished, water is injected for cleaning, and the cleaned sewage is discharged through the other first electric control valve 9 through the sewage discharge pipe;
after the cleaning is finished, one of the feeding connecting pipes 22 is connected with external hot air, and the hot air sequentially enters the heating stirring kettle 4, the temperature-adjusting stirring tank 3 and the mixing stirring tank 2 to be dried, so that the internal drying is ensured, and the moisture of each component is less than 0.1%.
Example 2
A waterborne polyurethane adhesive is prepared from the following components in parts by weight of 100: 9, mixing the part A and the part B, wherein the part A is prepared from the following raw materials in parts by weight: 115 parts of aromatic diisocyanate, 200 parts of polyether polyol, 170 parts of poly (1, 4-butanediol adipate) glycol, 34 parts of dimethylolpropionic acid, 19 parts of a salt forming agent, 2.5 parts of a chain extender and 69 parts of an organic solvent (the weight of each part is the same);
the part B is prepared from the following raw materials in parts by weight: 17.5 parts of aromatic diisocyanate, 17.5 parts of isophorone diisocyanate, 14 parts of polyether polyol, 24 parts of polyether polyol, 15 parts of polyether polyol, 4.5 parts of diethylene glycol and 39 parts of ethyl acetate (the same weight in each part);
step one, weighing aromatic diisocyanate, polyether polyol I and poly adipic acid-1, 4-butanediol ester diol, adding the weighed components into a stirring device, starting stirring, introducing nitrogen for protection, heating to 40 +/-1 ℃, adding a catalyst, gradually heating to 70 +/-1 ℃, stirring for reaction for 1 +/-0.1 hour, adding dimethylolpropionic acid, gradually heating to 80 +/-1 ℃, reacting for 2 +/-0.1 hour, then gradually heating to 90 +/-1 ℃, reacting for 3 +/-0.5 hour to enable the NCO mass fraction to reach 2.6-2.7%, and adding an organic solvent to prepare a prepolymer;
Step two, calculating the using amount of a chain extender and a salt former according to the mass fraction of NCO and the using amount of dimethylolpropionic acid, adding the chain extender and the salt former into deionized water for dispersion in advance, and then adding a prepolymer for full stirring and dispersion to prepare a part A;
step three, weighing the polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol, adding the weighed polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol into stirring equipment, heating the mixture to 70 +/-2 ℃, stirring the mixture for reaction for 1 +/-0.1 h, adding the polyether polyol IV, further reacting the mixture for 4 +/-0.5 h, measuring the mass fraction of NCO, adding ethyl acetate when the mass fraction reaches a theoretical value (7 +/-0.1%), continuing stirring, cooling and discharging the mixture to obtain a part B;
taking the part A and the part B in parts by weight as 100: (8.5-9.5), adding a certain amount of additives such as drying agents, flame retardants, coupling agents, antioxidants, ultraviolet inhibitors, coloring agents, adhesion promoters, fillers or plasticizers according to needs, placing the mixture into stirring equipment for stirring for 4 +/-1 min to obtain the waterborne polyurethane adhesive.
The stirring equipment used in the first step to the fourth step is the existing stirring device, namely the second step to the fourth step needs to adopt a plurality of stirring devices, is a production line type production mode, namely adopts a plurality of mutually independent stirring devices with the same or different specifications for stirring, is mutually independent, lacks linkage, cannot stably control temperature and time, has influence on the mixing effect, and simultaneously is a production line type production mode, and has long process, high energy consumption and large occupied area.
Example 3
A polyurethane adhesive is prepared from the following raw materials in parts by weight: 38 parts of castor oil, 11.75 parts of toluene diisocyanate, 49.75 parts of styrene and 0.5 part of dibenzoyl peroxide, and the components are melted and uniformly mixed by a multistage stirring device at the temperature of 20-80 ℃ to prepare the polyurethane adhesive.
Example 4
A polyurethane adhesive comprises a component A: 110 parts of toluene diisocyanate, 200 parts of modified resin and 39 parts of soluble ethyl acetate;
the component B comprises: 20 parts of modified hydroxyl compound of curing agent toluene diisocyanate; when the temperature of the components is controlled to be 30-90 ℃ by a multistage stirring device, the component A is taken: the weight ratio of the component B is 100:20, and the components are melted and uniformly mixed to prepare the polyurethane adhesive.
Comparative experiments were carried out on the polyurethane adhesives prepared in examples 1 to 4: wherein the comparison standard is as follows: production efficiency (production per unit time) and power consumption per unit; and other properties, and the results are shown in table 1 and are more intuitive.
The experimental table is as follows (table 1): wherein the test temperature for the tack-free time is 25 ℃.
Figure BDA0003676674520000191
From the experimental data in table 1 above, it can be seen that the mixing and stirring apparatus of example 1 is different from the mixing and stirring apparatus of example 2, which is prepared only in the first to fourth steps, and the aqueous polyurethane adhesive of example 2 is prepared; the production time is long, and the unit power consumption is high; other properties were slightly inferior to those of example 1.
In examples 3 and 4, the ratio of raw materials was different from that in example 1, but the production steps used were the same equipment, and the production time was short in examples 3 and 4, the power consumption per unit was low, and the other performance effects were poor.
The preparation method adopts the multistage stirring device for mixed production, and has short production time and high efficiency; the unit power consumption is low; the invention has scientific and reasonable raw material matching, good bonding effect, stable process and better market prospect;
the multistage stirring device has a compact structure, occupies a small area, realizes the simultaneous production of A, B parts, uniformly discharges materials, quickly stirs the materials, and has high efficiency and low energy consumption; heating stirred tank 4 and control heater 7 and a 6 cooperation on the section of thick bamboo that keeps warm guarantee the constant temperature stirring, and the agitator tank 3 that adjusts the temperature and the cooperation of a two 10 on the section of thick bamboo that keeps warm carry out effective rapid cooling to its 3 inside materials of agitator tank that adjust the temperature, guarantee the misce bene, and the stirring misce bene improves compounding efficiency, and the while is poured into mixing agitator tank 2 inside in proportion, carries out quick high strength stirring, and production efficiency is high.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments, or alternatives may be employed, by those skilled in the art, without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (10)

1. The preparation method of the waterborne polyurethane adhesive is characterized in that the waterborne polyurethane adhesive is prepared from the following components in parts by weight of 100: (8.5-9.5) and part B, wherein the part A is prepared by mixing the following raw materials in parts by weight: 110-115 parts of aromatic diisocyanate, 180-200 parts of polyether polyol, 150-170 parts of poly (1, 4-butanediol adipate) glycol, 29-34 parts of dimethylolpropionic acid, 14-19 parts of a salt forming agent, 0.6-2.5 parts of a chain extender and 66-69 parts of an organic solvent; the part B is prepared from the following raw materials in parts by weight: 16.5-17.5 parts of aromatic diisocyanate, 16.5-17.5 parts of isophorone diisocyanate, 11-14 parts of polyether glycol I, 11-14 parts of polyether glycol II, 21-24 parts of polyether glycol III, 13-15 parts of polyether glycol IV, 2.5-4.5 parts of diethylene glycol and 31-39 parts of ethyl acetate (the same weight in each part).
2. The method for preparing the waterborne polyurethane adhesive according to claim 1, wherein the method comprises the following steps:
step one, weighing aromatic diisocyanate, polyether polyol I and poly adipic acid-1, 4-butanediol ester diol, adding the weighed components into a stirring device, starting stirring, introducing nitrogen for protection, heating to 40 +/-1 ℃, adding a catalyst, gradually heating to 70 +/-1 ℃, stirring for reaction for 1 +/-0.1 hour, adding dimethylolpropionic acid, gradually heating to 80 +/-1 ℃, reacting for 2 +/-0.1 hour, then gradually heating to 90 +/-1 ℃, reacting for 3 +/-0.5 hour to enable the NCO mass fraction to reach 2.6-2.7%, and adding an organic solvent to prepare a prepolymer;
Step two, calculating the using amount of a chain extender and a salt former according to the mass fraction of NCO and the using amount of dimethylolpropionic acid, adding the chain extender and the salt former into deionized water for dispersion in advance, and then adding a prepolymer for full stirring and dispersion to prepare a part A;
step three, weighing the polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol, adding the weighed polyether polyol I, the polyether polyol II, the polyether polyol III, the aromatic diisocyanate, the isophorone diisocyanate and the diethylene glycol into stirring equipment, heating the mixture to 70 +/-2 ℃, stirring the mixture for reaction for 1 +/-0.1 h, adding the polyether polyol IV, further reacting the mixture for 4 +/-0.5 h, measuring the mass fraction of NCO, adding ethyl acetate when the mass fraction reaches a theoretical value (7 +/-0.1%), continuing stirring, cooling and discharging the mixture to obtain a part B;
taking the part A and the part B in parts by weight as 100: (8.5-9.5), adding a certain amount of additives such as drying agents, flame retardants, coupling agents, antioxidants, ultraviolet inhibitors, coloring agents, adhesion promoters, fillers or plasticizers according to needs, placing the mixture into a stirring device for stirring for 4 +/-1 min to obtain the waterborne polyurethane adhesive.
3. The method of claim 2, wherein the part A is a translucent milky white liquid having a solid content of 28 ± 0.5%, a viscosity of 13 ± 3mPa · s at 25 ℃, a pH of 7 ± 0.2, and a density of 1 ± 0.05 g/mL.
4. The method for preparing the aqueous polyurethane adhesive according to claim 2, wherein the part B is a colorless transparent viscous liquid with a solid content of 90 ± 0.5%, a viscosity of 11 ± 1 mPa-s at 25 ℃ and a density of 1.15 ± 0.05 g/mL.
5. The method for preparing the aqueous polyurethane adhesive according to claim 1, wherein the aqueous polyurethane adhesive is milky white, has a solid content of 33 ± 4%, a viscosity of 25 ± 5 mPa-s at 25 ℃, a density of 1.06 ± 0.01g/mL, and a pot life of 12 ± 0.5 h.
6. The preparation method of the waterborne polyurethane adhesive as claimed in claim 1, wherein the dimethylolpropionic acid is ground and pulverized by a grinding mechanism, the fineness of the dimethylolpropionic acid is not less than 80 meshes, and the molar ratio of the salt forming agent to the dimethylolpropionic acid is (0.73-0.78): 1.
7. the method for preparing the aqueous polyurethane adhesive according to claim 2, wherein the organic solvent is one of acetone, methyl ethyl ketone or N, N-dimethylformamide; the chain extender adopts one of 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, ethylenediamine, N-dihydroxy or aniline; the salt forming agent adopts one of triethylamine, methylamine, ethanolamine or dimethylethanolamine; the aromatic diisocyanate is one of toluene diisocyanate, diphenylmethane diisocyanate or 1, 5-naphthalene diisocyanate; the polyether polyol I, the polyether polyol II, the polyether polyol III and the polyether polyol IV respectively adopt one of polyoxypropylene diol, polytetrahydrofuran diol, polyoxytetramethylene diol, polyethylene glycol or polytetramethylene glycol; the catalyst in the first step adopts stannous octoate, lead octoate or dibutyltin dilaurate; and the pH value of the deionized water in the second step is 7 +/-0.1.
8. The method for preparing aqueous polyurethane adhesive according to claim 1, wherein the moisture content of each component of the B part is less than 0.1%.
9. The preparation method of the waterborne polyurethane adhesive according to claim 2, wherein the stirring device used in the first step to the fourth step is a multistage stirring device, the multistage stirring device comprises a mounting rack (1), a mixing stirring tank (2), two heat-preserving cylinders II (10), two heat-preserving cylinders I (6) and a plurality of grinding mechanisms (5) are sequentially arranged on the mounting rack (1) from bottom to top, the temperature-adjusting stirring tanks (3) are respectively arranged in the heat-preserving cylinders II (10), the heating stirring tanks (4) are respectively arranged on the heat-preserving cylinders I (6), the heaters (7) are arranged on the heat-preserving cylinders I (6), the heating stirring tanks (4) on the same side of the grinding mechanisms (5) are connected through flexible pipelines, the heating stirring tanks (4) are connected with the temperature-adjusting stirring tanks (3) on the same side through pipelines, the temperature-adjusting stirring tanks (3) are connected with the mixing stirring tank (2);
the mounting frame (1) comprises a base frame (16), a plurality of uniformly distributed support legs are arranged at the lower end of the base frame (16), a vertical frame and a plurality of circumferentially uniformly distributed protective guards (17) are arranged on the upper side of the base frame (16), a second mounting plate (18) is arranged on the front side of the vertical frame, two mounting holes are formed in the second mounting plate (18), a first mounting plate (19) is arranged at the upper end of the vertical frame, a walking frame (20) is arranged at the upper end of the first mounting plate (19), and a ladder stand (21) is arranged between the first mounting plate (19) and the vertical frame;
The heat preservation cylinder I (6) is fixed on a first mounting plate (19), a temperature sensor I (27) and a temperature sensor II (28) are arranged on a first mounting plate (18), the temperature sensor I (27) extends into the heating stirring kettle (4), a kettle cover is detachably arranged on the heating stirring kettle (4), a plurality of feeding connecting pipes (22) are arranged on the kettle cover, one feeding connecting pipe (22) is connected with an external water source, one feeding connecting pipe (22) is connected with external hot air, a protective cover (23) is arranged on the kettle cover, the lower end of the protective cover (23) is hinged on the heating stirring kettle (4), a stirring motor (24) is arranged on the protective cover (23), a first stirring frame is rotatably arranged on the kettle cover and is positioned inside the heating stirring kettle (4), a chain wheel pair is arranged between the first stirring frame and the stirring motor (24), the chain wheel pair is positioned on the inner side of the protective cover (23), an electric push rod (26) is hinged between the first heat-preservation cylinder (6) and the protective cover (23).
10. The preparation method of the aqueous polyurethane adhesive according to claim 9, wherein the grinding mechanism (5) comprises a limiting seat (38), the limiting seat (38) is sleeved on the traveling frame (20), the limiting seat (38) abuts against the lower side of the traveling frame (20), two symmetrical limiting wheels (44) are arranged inside the limiting seat (38), the limiting wheels (44) respectively abut against two sides of the traveling frame (20), an object placing barrel (37) is arranged at the upper end of the limiting seat (38), a traveling wheel (43) is rotatably arranged inside the object placing barrel (37), the traveling wheel (43) abuts against a groove of the traveling frame (20), a traveling motor (36) is fixed at the outer side of the object placing barrel (37), an output shaft of the traveling motor (36) is in transmission connection with the traveling wheel (43), a grinding barrel (35) is fixed at the upper end of the object placing barrel (37), a grinding motor (42) is fixed below the grinding barrel (35), be fixed with on the output shaft of grinding motor (42) and grind driving disk (41), the upper end spiro union of grinding vessel (35) has regulation spiral shell dish (33), the spiro union has locking screw (34) on grinding vessel (35), the tip of locking screw (34) is contradicted on regulation spiral shell dish (33), regulation spiral shell dish (33) lower extreme is equipped with grinds price fixing disc (40), regulation spiral shell dish (33) upper end is equipped with feeder hopper (31), be equipped with between feeder hopper (31) and regulation spiral shell dish (33) accuse gage board (32), the lateral part of grinding vessel (35) is equipped with bleeder valve (39), flexible conduit connects between bleeder valve (39) and feeding connecting pipe (22).
CN202210624885.7A 2022-06-02 2022-06-02 Preparation method of waterborne polyurethane adhesive Pending CN114774058A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101708441A (en) * 2009-11-17 2010-05-19 上海辛帕工业自动化有限公司 Two-component adhesive glue blending device
CN102806611A (en) * 2012-08-20 2012-12-05 湘潭方棱聚氨酯机器有限公司 Continuous automatic double-component adhesive mixing machine
CN103555259A (en) * 2013-10-31 2014-02-05 淄博德信联邦化学工业有限公司 Aqueous polyurethane adhesive and preparation method thereof
CN106978129A (en) * 2017-03-16 2017-07-25 惠州市亨迪树脂制品有限公司 A kind of high solids content double-component waterborne polyurethane adhesive with low-temperature activation and preparation method thereof
CN110538601A (en) * 2019-07-18 2019-12-06 中山市马里奥机械科技有限公司 production conveying system of polyurethane adhesive

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101708441A (en) * 2009-11-17 2010-05-19 上海辛帕工业自动化有限公司 Two-component adhesive glue blending device
CN102806611A (en) * 2012-08-20 2012-12-05 湘潭方棱聚氨酯机器有限公司 Continuous automatic double-component adhesive mixing machine
CN103555259A (en) * 2013-10-31 2014-02-05 淄博德信联邦化学工业有限公司 Aqueous polyurethane adhesive and preparation method thereof
CN106978129A (en) * 2017-03-16 2017-07-25 惠州市亨迪树脂制品有限公司 A kind of high solids content double-component waterborne polyurethane adhesive with low-temperature activation and preparation method thereof
CN110538601A (en) * 2019-07-18 2019-12-06 中山市马里奥机械科技有限公司 production conveying system of polyurethane adhesive

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