CN109824913B - Continuous dispersion system for preparing aqueous polyurethane dispersion and continuous dispersion process and application thereof - Google Patents

Abstract

The invention belongs to the technical field of continuous production of aqueous polyurethane dispersions, and particularly relates to a continuous dispersion system for preparing an aqueous polyurethane dispersion, a continuous dispersion process and application thereof; the continuous dispersion system comprises: the pipe type disperser is provided with a feed inlet and a plurality of water inlets; the continuous dispersion system further comprises: the motor and a plurality of tooth row type dispersion discs driven by the motor and positioned on the central shaft of the inner cavity of the tubular disperser. The system can realize the dispersion of high-viscosity ionomer, realize the rapid and efficient continuous production, is suitable for the application of a plurality of varieties, and has stable quality and narrow particle size distribution of the obtained product.

Description

Continuous dispersion system for preparing aqueous polyurethane dispersion and continuous dispersion process and application thereof

Technical Field

The invention belongs to the technical field of continuous production of aqueous polyurethane dispersions, and particularly relates to a continuous dispersion system for preparing an aqueous polyurethane dispersion, a continuous dispersion process and application thereof.

Background

The aqueous polyurethane dispersion takes water as a dispersion medium instead of an organic solvent, does not contain a volatile organic solvent (VOC), and is a tasteless, nontoxic, green and environment-friendly organic polymer material. The water is volatilized in the using process to form a polyurethane film, so that the film-forming material of the aqueous polyurethane dispersion has excellent physical and chemical properties which are equal to those of a polyurethane material.

The waterborne polyurethane material can be prepared into high-performance materials with different hardness and chemical resistance by adjusting a formula and a chemical modification mode, and can be widely applied to the fields of wood coatings, textile coatings, synthetic leather, plastic coatings, metal coatings, personal care, coating agents, adhesives, sealants, water-based ink and the like.

At present, the industrial production process of aqueous polyurethane dispersions is based on a batch process. The batch process refers to a process in which the processes of prepolymerization, dispersion and solvent removal are carried out in a reaction kettle step by step according to a time sequence after one-time feeding. However, the batch process has significant disadvantages in the production of aqueous polyurethane dispersions, in particular as follows: (1) the production efficiency is low, the vacancy rate of the device is high, and the production cost is high; (2) the production excessively depends on manual work, and the automation degree is low; (3) the quality fluctuation among product batches is large, and the defective rate is high.

The continuous production process of the aqueous polyurethane dispersion can effectively overcome the problems caused by intermittent production, and patent document CN102633971A discloses a continuous production process of the aqueous polyurethane dispersion based on the design of a double-screw reactor, wherein the continuous production process of the aqueous polyurethane dispersion adopts the processes of high-temperature prepolymerization at 120-200 ℃ and high-temperature dispersion at 90-150 ℃; for a water-based polyurethane system, high-temperature pre-polymerization can bring unpredictable side reactions, the macromolecular structure is uncontrollable, high-temperature dispersion can cause that the particle size control is very difficult when emulsion is dispersed, and the finished emulsion can be obtained only by cooling due to higher temperature of the whole process, and the production cost is high due to high process energy consumption. Patent document WO2017/009161a1 discloses a continuous dispersing device based on a static mixer, but the continuous dispersing of the static mixer requires the use of a large amount of a diluting solvent, and is only suitable for medium and low viscosity systems, and is not suitable for dispersing high viscosity systems (the viscosity of an ionomer is more than 10 ten-thousand cp), while the dispersing process of the waterborne polyurethane, particularly the phase transition process, is generally high in viscosity, and greatly limits the application of the static mixer to the waterborne polyurethane.

In addition, simple dispersers are not advantageous for the internal emulsified polymer ionomer systems, and generally require high-strength, rapid continuous dispersion to obtain an aqueous polyurethane dispersion, which is extremely unstable and very prone to settling. Therefore, it is an important research subject to explore a continuous dispersion system and a continuous dispersion process suitable for the aqueous polyurethane dispersion.

Disclosure of Invention

The invention aims to provide a continuous dispersion system for preparing aqueous polyurethane dispersoid, a continuous production process carried out by the system can realize the dispersion of high-viscosity ionomer (prepolymer), is suitable for the rapid and efficient continuous production of a plurality of varieties of aqueous polyurethane dispersoids, completely realizes automation, and has low production cost and energy consumption; meanwhile, the obtained dispersion product has stable quality and narrow particle size distribution.

In order to achieve the purpose, the technical scheme of the invention is as follows:

in one aspect of the present invention, there is provided a continuous dispersion system for preparing an aqueous polyurethane dispersion comprising:

the tubular disperser 1 is used for dispersing the waterborne polyurethane prepolymer in the dispersing water to prepare a waterborne polyurethane dispersion; the tubular disperser 1 is provided with a feed inlet 2 and a plurality of (for example, 10) water inlets, the water inlets are uniformly distributed along the axial direction of the tubular disperser 1, and the water inlets are used for introducing dispersing water into the tubular disperser 1; in some examples, the feed inlet 2 is positioned at the top of one end of the tubular disperser and is used for feeding the aqueous polyurethane prepolymer into the tubular disperser 1; the water inlets are uniformly arranged on the wall of the disperser along the axial direction of the tubular disperser 1 at equal intervals.

The continuous dispersion system further comprises: the dispersing device comprises a motor 4, a middle shaft 5 positioned in the inner cavity of the tubular disperser 1 and a plurality of tooth-row dispersing disks 6 inserted in the middle shaft, wherein the middle shaft 5 is distributed along the axial direction of the tubular disperser, one end of the middle shaft is connected with the motor 4, and the other end of the middle shaft is fixed on the inner wall of the tubular disperser 1.

In the continuous dispersion system, a motor 4 drives a middle shaft to rotate, and a plurality of dentition type dispersion discs 6 arranged on a middle shaft 5 fully mix the waterborne polyurethane prepolymer and the dispersion water in a tubular disperser 1.

According to the continuous dispersing system provided by the invention, in some preferred embodiments, the length-diameter ratio of the tubular disperser 1 is 5-105. According to the three stages of the phase transition principle in the preparation process of the aqueous polyurethane dispersion, in some preferred embodiments, two inner partition plates 7 are arranged in the tubular disperser 1, and the inner cavity of the tubular disperser is divided into three areas, which are a premixing area, a phase transition area and a dilution area in sequence along the axial direction.

Preferably, a plurality of irregular openings are formed in the inner partition plate 7; on each inner partition plate, the sum of the areas of the openings accounts for 15-75% of the total area of the inner partition plate, such as 20%, 30%, 40%, 50% and 60%;

preferably, the distance between the two inner partition plates 7 and the feed inlet 2 is 1/4 and 7/8 of the length of the tubular disperser cavity, respectively.

In some examples, the number of the dentition dispersion boards 6 arranged in the premixing area is 2-11, for example, 3, 5, 8, 10; the number of the dentition type dispersion discs 6 arranged in the phase transition region is 3-38, for example, 5, 10, 15, 20 and 30; the number of the tooth array type dispersion discs 6 arranged in the dilution zone is 1-5, for example, 2 or 4; the total number of tooth row type dispersion discs conforms to the following formula: 7< X + Y + Z < 50; in the formula, X, Y, Z represents the number of tooth row type dispersion plates in the premixing area, the phase transition area and the dilution area in turn.

It will be appreciated by those skilled in the art that the tooth array dispersing disks 6 may be of many different types. In some examples, the serrated dispersion plate 6 is a serrated dispersion plate having an inner hole or a serrated dispersion plate not having an inner hole; each dentition dispersion plate with inner holes can be provided with a plurality of inner holes, and the sum of the areas of the inner holes accounts for 0-87% of the total area of the dentition dispersion plate, for example, 5%, 10%, 15%, 20%, 25%, 40%, 50%, 60%, 70% and 80%. In some preferred embodiments, a plurality of regularly distributed inner holes and/or irregularly distributed inner holes are arranged on the dentition dispersion plate; or a plurality of regular inner holes and/or irregular inner holes which are not uniformly distributed are/is arranged on the dentition type dispersion plate.

In some examples, the tubular disperser 1 is further provided with a metering pump, and each water inlet is connected with one metering pump and used for quantitatively and continuously injecting the dispersing water into a plurality of water inlets simultaneously; preferably, the metering pump is a positive displacement pump. In the present invention, the metering pump is well known to those skilled in the art, and the operation and performance parameters of the apparatus are all conventionally selected.

The working principle of the continuous dispersion system provided by the invention is as follows: the continuous production process of the aqueous polyurethane dispersion is carried out by adopting a continuous dispersion system consisting of a tubular disperser, the aqueous polyurethane prepolymer is added at a feed inlet positioned at one end part (for example, the head end) of the tubular disperser in one step, the dispersed water is added into the tubular disperser in multiple times in different amounts according to the phase transition principle, and the dispersion and emulsification are carried out under the violent stirring action of a dispersion disc, so that the aqueous polyurethane dispersion is obtained.

In another aspect of the present invention, there is provided a continuous dispersion process for the preparation of an aqueous polyurethane dispersion using the continuous dispersion system as described above, the continuous dispersion process comprising the steps of:

continuously adding the aqueous polyurethane prepolymer solution containing the solvent and the dispersing water into the tubular disperser 1, and fully mixing the mixture of the aqueous polyurethane prepolymer solution and the dispersing water under the action of the dentition type dispersing disc 6 to obtain the aqueous polyurethane dispersion containing the solvent. Fully mixing the aqueous polyurethane prepolymer solution and the dispersion water to complete phase transition under the action of an inner tooth array type dispersion disc of the tubular disperser, and obtaining the aqueous polyurethane dispersion containing the solvent after dispersion and emulsification. Preferably removing the solvent to obtain the aqueous polyurethane dispersion. In the present invention, the removal of the solvent is a routine operation in the art.

In the invention, the aqueous polyurethane prepolymer can be obtained by adopting the conventional technology in the field. It will be understood by those skilled in the art that the preparation of the aqueous polyurethane prepolymer may be carried out in a batch reactor or a continuous tubular reactor. In some examples, the aqueous polyurethane prepolymer solution is prepared by an acetone method or a prepolymer method. The preparation of the aqueous polyurethane prepolymer by the acetone method or the prepolymer method is well known to those skilled in the art; it will be appreciated by those skilled in the art that the preparation of the prepolymer may be carried out in one tubular reactor or in a plurality of tubular reactors connected in series. In some examples, the tubular reactor used can be a spherical tubular reactor with an internal baffle plate, the length-diameter ratio of the tubular reactor is 10-500, and the pressure drop of an inlet and an outlet of the tubular reactor is less than 0.05 MPa; the inner baffle is arranged at the spherical diameter 1/4-1/2 close to the inlet of the spherical tubular reactor; preferably, a plurality of uniformly distributed circular holes are formed in the inner baffle, and the sum of the areas of the circular holes accounts for 25-78% of the total area of the inner baffle.

In a preferred embodiment, the aqueous polyurethane prepolymer solution is prepared by contacting and reacting polyisocyanate with oligomer polyol, a non-ionic hydrophilic compound, small molecular diol, small molecular diamine, an ionic hydrophilic chain extender, a neutralizer and a solvent.

Preferably, the polyisocyanate is an aliphatic diisocyanate and/or an aromatic diisocyanate, more preferably one or more selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

Preferably, the oligomer polyol is selected from one or more of polyester diol, polyether diol and polycarbonate diol; more preferably, the number average molecular weight of the polyester diol is 200-5000, and the polyester diol is selected from one or more of polybutylene adipate diol, neopentyl glycol adipate diol, polyhexamethylene glycol adipate diol, polycaprolactone diol, polyhexamethylene glycol phthalate diol and neopentyl glycol phthalate diol; more preferably, the polyether diol has the number average molecular weight of 200-5000, and is selected from one or more of polyoxypropylene diol, copolymerized diol of polyoxyethylene and polyoxypropylene and polytetrahydrofuran diol; more preferably, the polycarbonate diol has the number average molecular weight of 200-5000, and is prepared from carbonic acid diester and diol ester through ester exchange reaction.

Preferably, the non-ionic hydrophilic compound is a hydrophilic polyether compound containing a monofunctional or difunctional group reactive with isocyanate groups, more preferably selected from compounds containing a polyethoxy segment and having an ethylene oxide number of 12 to 75 per molecule, and having a molar mass of 500-3000 g/mol.

Preferably, the small molecule diol is selected from one or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, neopentyl glycol and cyclohexanedimethanol.

Preferably, the small molecule diamine is selected from one or more of isophoronediamine, butanediamine, ethylenediamine, 1, 6-hexanediamine, piperazine, 1, 4-diaminocyclohexane, bis- (4-aminocyclohexyl) methane, adipic acid dihydrazide and hydrazine.

Preferably, the hydrophilic chain extender is selected from a dihydroxy compound containing hydrophilic groups, a diamino compound containing sulfonic acid, or a diamino compound containing sulfonate salts; the hydrophilic group-containing dihydroxy compound is preferably selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid and dihydroxysuccinic acid; the sulfonic acid-containing diamino compound or sulfonate-containing diamino compound is preferably selected from the group consisting of N- (2-aminoethyl) -2-aminoethanesulfonic acid, alkali metal N- (2-aminoethyl) -2-aminoethanesulfonic acid, ammonium N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -2-aminoethanesulfonic acid, alkali metal N- (3-aminopropyl) -2-aminoethanesulfonic acid, ammonium N- (3-aminopropyl) -3-aminopropanesulfonic acid, alkali metal N- (2-aminoethyl) -2-aminoethanesulfonic acid, alkali metal N- (3-aminopropyl) -3-aminopropanesulfonic acid, alkali metal N- (2-aminoethanesulfonic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid, ammonium salt thereof, N- (3-aminopropyl) -2-aminoethanesulfonic acid, N- (3-aminoethanesulfonic acid, N-amino-sulfonic acid, N-sulfonic acid salt thereof, N- (3-amino-propyl) -2-aminoethanesulfonic acid, N-sulfonic acid salt thereof, N-amino-sulfonic acid, N-sulfonic acid salt thereof, N-2-amino-sulfonic acid salt thereof, and salt thereof, One or more of N- (3-aminopropyl) -3-aminopropanesulfonic acid ammonium salt, N- (2-aminoethyl) -3-aminopropanesulfonic acid alkali metal salt and N- (2-aminoethyl) -3-aminopropanesulfonic acid ammonium salt.

Preferably, the neutralizing agent is selected from one or more of ammonia, ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, morpholine, N-methylmorpholine, dimethylisopropylamine, N-methyldiethanolamine, triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide.

Preferably, the solvent is selected from butanone and/or acetone.

In some preferred embodiments, the aqueous polyurethane prepolymer solution is added into the tubular disperser 1 through the feed inlet 2 at a constant speed and in a fixed amount; the dispersion water is simultaneously added into the tubular disperser 1 through a plurality of evenly distributed water inlets.

In some preferred embodiments, the number of the water inlets is ten, and the water inlets are respectively a first water inlet W1, a second water inlet W2, a third water inlet W3, a fourth water inlet W4, a fifth water inlet W5, a sixth water inlet W6, a seventh water inlet W7, an eighth water inlet W8, a ninth water inlet W9 and a tenth water inlet W10, and the dispersing water is simultaneously added to the tubular disperser 1 by a metering pump connected to each water inlet in the following ratio:

the mass of the dispersing water added into the first water inlet W1 accounts for 3-35% of the total added mass, such as 5%, 10%, 15%, 20%, 30%, the mass of the dispersing water added into the second water inlet W2 accounts for 3-35% of the total added mass, such as 5%, 10%, 15%, 20%, 30%, the mass of the dispersing water added into the third water inlet W3 accounts for 0-15% of the total added mass, such as 5%, 10%, 12%, the mass of the dispersing water added into the fourth water inlet W4 accounts for 0-15% of the total added mass, such as 5%, 10%, 12%, the mass of the dispersing water added into the fifth water inlet W5 accounts for 0-15% of the total added mass, such as 5%, 10%, 12%, the mass of the dispersing water added into the sixth water inlet W6 accounts for 0-15% of the total added mass, such as 5%, 10%, 12%, the mass of the dispersed water added into the seventh water inlet W7 accounts for 0-15%, for example, 5%, 10%, 12% of the total added mass, the mass of the dispersed water added into the eighth water inlet W8 accounts for 5-30%, for example, 5%, 10%, 15%, 20%, 25% of the total added mass, the mass of the dispersed water added into the ninth water inlet W9 accounts for 5-30%, for example, 5%, 10%, 15%, 20%, 25% of the total added mass, and the mass of the dispersed water added into the tenth water inlet W10 accounts for 5-30%, for example, 5%, 10%, 15%, 20%, 25% of the total added mass.

In accordance with the continuous dispersion process provided herein, in some examples, the dispersion process conditions of the mixture within the tubular disperser 1 include: the dispersion rotation speed is 500-3000 r/min (such as 800r/min, 1000r/min, 2000r/min, 2500r/min), the reaction temperature is 5-35 ℃ (such as 10 ℃, 20 ℃, 30 ℃) and the reaction pressure is 0.1-1MPa (such as 0.2MPa, 0.5MPa, 0.8 MPa); the flow rate of the mixture is 0.1 to 10m/min (e.g., 0.5m/min, 1.0m/min, 5m/min, 8m/min), and the residence time of the mixture is 10 to 300 seconds (e.g., 20 seconds, 50 seconds, 100 seconds, 200 seconds).

Preferably, the mass ratio of the aqueous polyurethane prepolymer solution to the dispersion water in the mixture is 1: 0.2-1: 3, for example, 1:0.3, 1:0.5, 1:1, 1:1.5, 1:2, 1: 2.5.

The continuous dispersion system and the continuous dispersion process of the waterborne polyurethane can realize full-automatic control, have high production efficiency, stable product quality and wide application range, and are suitable for preparing various waterborne polyurethane dispersions, such as waterborne polyurethane production by an acetone method and waterborne polyurethane production by a prepolymer method.

The invention also provides the application of the continuous dispersion process in the production of aqueous polyurethane by an acetone method, the production of aqueous polyurethane by a prepolymer method, the preparation process of aqueous polyurethane acrylate dispersoid and the preparation process of light-curable aqueous polyurethane acrylate dispersoid.

The aqueous polyurethane dispersions produced by the continuous production process described above can be used in wood coatings, textile coatings, synthetic leather, plastic coatings, metal coatings, personal care, coating agents, adhesives, and sealants.

The technical scheme of the invention has the beneficial effects of the following aspects:

1) compared with an intermittent preparation device and process, the continuous dispersion process of the aqueous polyurethane dispersion disclosed by the invention adopts a continuous dispersion system comprising a tubular disperser, can disperse a high-viscosity prepolymer (suitable for the prepolymer with the maximum dispersion viscosity of 80 wcp), is suitable for preparing solvent-free or small-amount solvent-free aqueous polyurethane (such as example 3), and is high in production efficiency and low in energy consumption.

2) In order to prevent the dispersion body from back mixing in the dispersing process, two inner partition plates are arranged in the tubular disperser to divide the inner cavity of the tubular disperser into three areas (a premixing area, a phase transition area and a diluting area respectively), and the distribution of the number of the dispersion discs also conforms to the three stages mentioned in the phase transition principle, so that the arrangement is very favorable for the efficient dispersion of the prepolymer; in addition, the dispersion plate is a tooth array type dispersion plate with an inner hole, and the pressure in the disperser can be reduced while the dispersion is strengthened; the design ensures that the tubular disperser has high-efficiency dispersing capacity, very low pressure drop (the pressure drop of the inlet and the outlet is less than 0.2Mpa), low energy consumption, wide applicable range and various production types.

3) In the continuous dispersion process of the aqueous polyurethane dispersion, the dispersion with narrow particle size distribution and stability can be obtained by simultaneously introducing the unequal addition process of the dispersion water through a plurality of water inlets; when the aqueous polyurethane dispersion prepared by the method is used for wood lacquer or adhesive, the mechanical stability, the thermal storage stability and the brushing property are excellent.

Drawings

FIG. 1 is a schematic illustration of a continuous dispersion system for preparing an aqueous polyurethane dispersion in one example of the present invention;

FIG. 2 is a schematic view of an internal baffle in the continuous dispersion system shown in FIG. 1.

In the above figures, the reference numerals are explained as follows:

1-tubular disperser, 2-feed inlet, 3-discharge outlet, 4-motor, 5-middle shaft, 6-dentition type dispersing disk and 7-inner partition plate;

w1-a first water inlet, W2-a second water inlet, W3-a third water inlet, W4-a fourth water inlet, W5-a fifth water inlet, W6-a sixth water inlet, W7-a seventh water inlet, W8-an eighth water inlet, W9-a ninth water inlet, and W10-a tenth water inlet.

Detailed Description

In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.

< sources of reaction raw materials >

HDI, (hexamethylene diisocyanate), wanhua chemistry, industrial;

TDI-80 (toluene diisocyanate-80), Hebei Dazhou, Industrial product;

IPDI (isophorone diisocyanate), degussa corporation, industrial;

PTMEG2000 (polytetrahydrofuran diol, Mn 2000), shanxi, san xie, a commercial product;

PBA2000 (polybutylene adipate glycol, Mn ═ 2000), Qingdao yutian, industrial;

PCL2000 (polycaprolactone diol, Mn 2000), Qingdao yutian, industrial;

PNA2000 (poly neopentyl glycol adipate diol, Mn ═ 2000), Qingdao yutian, industrial;

MPEG520 (monohydroxypolyethylene oxide, Mn 500), austenitizer, industrial;

DMPA (dimethylolpropionic acid), boston, sweden, industrial;

BDO (1, 4-butanediol), Mitsubishi chemical industry, Industrial products;

catalyst (dibutyltin dilaurate (T12)), chemical engineering, industrial products of shanghai yutian;

triethylamine, Zhejiang construction industry and industrial products;

ethylenediamine, yankee basf, industrial;

n- (2-aminoethyl) -2-aminoethane sodium sulfonate, winning creations of chemicals and industrial products.

< test methods >

1. Particle size and particle size distribution index test

The particle size and the particle size distribution of the aqueous polyurethane dispersion emulsion are detected by a laser particle size analyzer (ZS90, Malvern), and a detection sample needs to be uniformly diluted to a certain concentration.

2. Brushing test

1) The preparation process of the coating (adhesive) comprises the following steps: 100g of the aqueous polyurethane dispersion and 0.05g of BYK024 (Pico chemical) were mixed, stirred at 500rpm for 5min, 0.2g of Tego245 (digao) was added, stirred for 5min, then 0.15g of Vesmody U604 (Vasmody chemical) was added, and stirred at 600rpm for 10min to obtain the final product.

2) Preparation and testing of test specimens

Placing a rubber strip on a wood board, placing the wood board and the rubber strip in a 70 ℃ oven, pre-polymerizing for 1 minute, taking out the rubber strip, coating the coating prepared in the step 1) on the rubber strip by using a wool brush, sensing the smoothness of coating, and observing whether the brush is formed.

3. Storage stability test

And (3) filling the aqueous polyurethane dispersion emulsion into a transparent sealed tank, recording the initial state, standing at normal temperature for 6 months, and observing whether the emulsion is layered, thickened, gelatinized and settled during storage. The occurrence of one of the above four phenomena is manifested as an unstable emulsion.

4. Heat storage stability test

And (3) putting the aqueous polyurethane dispersion emulsion into a transparent sealed tank, recording the initial state, placing the aqueous polyurethane dispersion emulsion in a 50 ℃ oven, wherein the storage is 1 month, and observing whether the emulsion is layered, thickened, gelatinized and settled during the storage. The occurrence of one of the above four phenomena is manifested as an unstable emulsion.

Continuous dispersion system for preparing aqueous polyurethane dispersion I:

as shown in fig. 1, comprises a tubular disperser 1, a motor 4 and a central shaft 5; the length-diameter ratio of the tubular disperser 1 is 95, the inner cavity of the tubular disperser 1 is divided into three areas (which are a premixing area, a phase transition area and a diluting area in sequence) by two inner partition plates 7, and the tubular disperser 1 is provided with a feed inlet 2 and ten water inlets; the distance between the two inner partition plates 7 and the feed inlet 2 is 1/4 and 7/8 of the length of the cavity of the tubular disperser respectively; the inner partition plate 7 is provided with 4 openings as shown in fig. 2, and the sum of the areas of the openings accounts for 60% of the total area of the inner partition plate; 12 dentition type dispersion discs 6 are inserted on the middle shaft 5 in a penetrating manner, wherein the number of the dentition type dispersion discs 6 arranged in the premixing area is 2, the number of the dentition type dispersion discs 6 arranged in the phase transition area is 8, and the number of the dentition type dispersion discs 6 arranged in the dilution area is 2. The dentition type dispersion plate 6 is a dispersion plate with inner holes, 3 inner holes are arranged on the plate body, and the sum of the areas of the inner holes accounts for 62% of the total area of the dentition type dispersion plate.

Continuous dispersion system for preparing aqueous polyurethane dispersion II:

as shown in fig. 1, comprises a tubular disperser 1, a motor 4 and a central shaft 5; the length-diameter ratio of the tubular disperser 1 is 95, the inner cavity of the tubular disperser 1 is divided into three areas (which are a premixing area, a phase transition area and a diluting area in sequence) by two inner partition plates 7, and the tubular disperser 1 is provided with a feed inlet 2 and ten water inlets; the distance between the two inner partition plates 7 and the feed inlet 2 is 1/4 and 7/8 of the length of the cavity of the tubular disperser respectively; the inner partition plate 7 is provided with 4 openings as shown in fig. 2, and the sum of the areas of the openings accounts for 60% of the total area of the inner partition plate; the middle shaft 5 is inserted with 8 dentition type dispersion discs 6, wherein the number of the dentition type dispersion discs 6 arranged in the premixing area is 2, the number of the dentition type dispersion discs 6 arranged in the phase transition area is 5, and the number of the dentition type dispersion discs 6 arranged in the dilution area is 1. The dentition type dispersion plate 6 is a dispersion plate with inner holes, 5 inner holes are arranged on the plate body, and the sum of the areas of the inner holes accounts for 74% of the total area of the dentition type dispersion plate.

Continuous dispersion system III for preparing aqueous polyurethane dispersions:

as shown in fig. 1, comprises a tubular disperser 1, a motor 4 and a central shaft 5; the length-diameter ratio of the tubular disperser 1 is 95, the inner cavity of the tubular disperser 1 is divided into three areas (which are a premixing area, a phase transition area and a diluting area in sequence) by two inner partition plates 7, and the tubular disperser 1 is provided with a feed inlet 2 and ten water inlets; the distance between the two inner partition plates 7 and the feed inlet 2 is 1/4 and 7/8 of the length of the cavity of the tubular disperser respectively; the inner partition plate 7 is provided with 4 openings as shown in fig. 2, and the sum of the areas of the openings accounts for 60% of the total area of the inner partition plate; the central shaft 5 is inserted with 7 dentition type dispersion discs 6, wherein the number of the dentition type dispersion discs 6 arranged in the premixing area is 1, the number of the dentition type dispersion discs 6 arranged in the phase transition area is 4, and the number of the dentition type dispersion discs 6 arranged in the dilution area is 1. The dentition type dispersion plate 6 is a dispersion plate with inner holes, 6 inner holes are arranged on the dentition type dispersion plate, and the sum of the areas of the inner holes accounts for 81 percent of the total area of the dentition type dispersion plate.

In comparative example 1 corresponding to each example, the process conditions for preparing the waterborne polyurethane by using the online disperser IKA (Ika) DR/DRS2000 include:

the dispersion machine is an online dispersion machine (type of Aika DR/DRS 2000), firstly, the temperature of the aqueous polyurethane prepolymer solution is controlled to be 35 ℃, the dispersion water is normal temperature water, the dispersion machine is started, the rotating speed is controlled to be 5000r/min, the aqueous polyurethane prepolymer and the dispersion water are simultaneously pumped into the online dispersion machine according to the mass ratio, phase transformation is completed to obtain aqueous polyurethane crude emulsion, and a rotary evaporator is used for removing acetone to obtain the aqueous polyurethane emulsion.

In comparative example 2 corresponding to each example, the process conditions for preparing the waterborne polyurethane by using the traditional intermittent dispersion machine include:

the dispersion machine selects a dentition dispersion disc type stirrer (Kecai FL22 model), firstly, the aqueous polyurethane prepolymer solution is put into a dispersion barrel, and the temperature is controlled at 35 ℃; the dispersion water is normal temperature water, the rotating speed of a dispersion disc is controlled at 1500r/min, the dispersion water is uniformly added into a dispersion barrel within 10min according to the mass ratio to complete phase transformation to obtain aqueous polyurethane crude emulsion, and a rotary evaporator is used for removing acetone to obtain the aqueous polyurethane emulsion.

Example 1

1. Preparing a water-based polyurethane prepolymer solution: adding 600 parts by weight of TDI-80, 50 parts by weight of acetone and 2000 parts by weight of PTMEG2000 into a tubular reactor, mixing, reacting at 85 ℃ for 30 minutes, then adding 120 parts by weight of DMPA, 70 parts by weight of BDO, 310 parts by weight of acetone and 1 part by weight of dibutyltin dilaurate catalyst, continuing to react at 75 ℃ for 1 hour, then adding 1100 parts by weight of acetone and 73 parts by weight of triethylamine, and reacting at 35 ℃ for 10 minutes to obtain the aqueous polyurethane prepolymer solution.

2. Preparing a water-based polyurethane dispersion coarse emulsion: the dispersion of the waterborne polyurethane prepolymer in the dispersion water is carried out by adopting a continuous dispersion system I, which specifically comprises the following steps:

adding 4323 parts by weight of the aqueous polyurethane prepolymer solution prepared in the step 1 into a tubular disperser 1 from a feed inlet 2, and simultaneously adding dispersed water into the tubular disperser 1 from ten water inlets, wherein the method comprises the following specific steps: 646 parts by weight of dispersion water is metered by a metering pump and then is added from a first water inlet W1, 445 parts by weight of dispersion water is metered by a metering pump and then is added from a second water inlet W2, 463 parts by weight of dispersion water is metered by a metering pump and then is added from a third water inlet W3, 463 parts by weight of dispersion water is metered by a metering pump and then is added from a fourth water inlet W4, 383 parts by weight of dispersion water is metered by a metering pump and then is added from a fifth water inlet W5, 383 parts by weight of dispersion water is metered by a metering pump and then is added from a sixth water inlet W6, 383 parts by weight of dispersion water is metered by a metering pump and then is added from a seventh water inlet W7, 383 parts by weight of dispersion water is metered by a metering pump and then is added from an eighth water inlet W8, 383 parts by weight of dispersion water is metered by a metering pump and then is added from a ninth water inlet W9, 468 parts by weight of dispersion water is metered by a metering pump and then is added from a decimal water inlet W10.

The dispersing process conditions of the mixture in the tubular disperser 1 comprise: the pressure drop of the inlet and the outlet is less than 0.2 Mpa; the dispersion rotating speed is 2100r/min, the reaction temperature is 23 ℃, and the reaction pressure is 0.3 Mpa; the flow rate of the mixture is 0.9m/min, the residence time of the mixture is 120 seconds, crude emulsion of the aqueous polyurethane dispersion is obtained, the crude emulsion is discharged from a discharge port 3 of the tubular disperser, and acetone is removed by a rotary evaporator (50 ℃, acetone removal is carried out at 1000 pa), and then aqueous polyurethane dispersion emulsion is obtained.

Comparative example 1 of example 1

1. The preparation of the aqueous polyurethane prepolymer solution is the same as that of example 1;

2. preparing a water-based polyurethane dispersion coarse emulsion: and (2) selecting an IKA (IKA) online dispersing machine DR/DRS2000, dispersing the aqueous polyurethane prepolymer solution prepared in the step (1) in dispersing water, adding 4323 parts of prepolymer at one time, adding 4400 parts of dispersing water at one time, shearing at high speed to obtain aqueous polyurethane dispersion coarse emulsion, and removing acetone to obtain aqueous polyurethane dispersion emulsion. The parts added in the above reaction materials are parts by weight.

Comparative example 2 of example 1

1. The preparation of the aqueous polyurethane prepolymer solution is the same as that of example 1;

2. preparing a water-based polyurethane dispersion coarse emulsion: dispersing the aqueous polyurethane prepolymer solution prepared in the step 1 in dispersion water by adopting traditional intermittent dispersion, wherein 4323 parts of prepolymer is added at one time, 4400 parts of dispersion water is added into the prepolymer at one time within 6min, and the prepolymer is subjected to high-speed shearing dispersion by a dispersion disc to obtain aqueous polyurethane dispersion coarse emulsion, and removing acetone to obtain aqueous polyurethane dispersion emulsion. The parts added in the above reaction materials are parts by weight.

Example 2

1. Preparing a water-based polyurethane prepolymer solution: 150 parts of HDI, 140 parts of IPDI (isophorone diisocyanate), 240 parts of acetone, 2100 parts of PBA2000, 50 parts of MPEG520 and 2 parts of dibutyltin dilaurate catalyst are added into a tubular reactor to be mixed, and the mixture is reacted for 3 hours at 75 ℃, 3000 parts of acetone is added and stirred for 0.5 hour, 31 parts of ethylenediamine, 32 parts of N- (2-aminoethyl) -2-aminoethane sodium sulfonate and 240 parts of water are added, and the reaction is continued for 20 minutes at 45 ℃ to obtain a waterborne polyurethane prepolymer solution.

2. Preparing a water-based polyurethane dispersion coarse emulsion: the continuous dispersion system II is adopted for dispersing the waterborne polyurethane prepolymer in the dispersion water, and specifically comprises the following steps:

5985 parts by weight of the aqueous polyurethane prepolymer solution prepared in the step 1 is added into a tubular disperser 1 from a feed inlet 2, and dispersed water is simultaneously added into the tubular disperser 1 from ten water inlets, and the method comprises the following specific steps: 346 parts by weight of dispersion water was metered by a metering pump and then fed from a first water inlet W1, 345 parts by weight of dispersion water was metered by a metering pump and then fed from a second water inlet W2, 300 parts by weight of dispersion water was metered by a metering pump and then fed from a third water inlet W3, 285 parts by weight of dispersion water was metered by a metering pump and then fed from a fourth water inlet W4, 263 parts by weight of dispersion water was metered by a metering pump and then fed from a fifth water inlet W5, 212 parts by weight of dispersion water was metered by a metering pump and then fed from a sixth water inlet W6, 150 parts by weight of dispersion water was metered by a metering pump and then fed from a seventh water inlet W7, 150 parts by weight of dispersion water was metered by a metering pump and then fed from an eighth water inlet W8, 150 parts by weight of dispersion water was metered by a metering pump and then fed from a ninth water inlet W9, 399 parts by weight of dispersion water was metered by a metering pump and then fed from a tenth water inlet W10.

The dispersing process conditions of the tubular disperser (1) comprise: the pressure drop of the inlet and the outlet is less than 0.2 Mpa; the dispersion speed is 1500r/min, the reaction temperature is 24 ℃, and the reaction pressure is 0.4 Mpa; the flow rate of the mixture is 2m/min, the retention time of the mixture is 60 seconds, crude emulsion of the aqueous polyurethane dispersion is obtained, the crude emulsion is discharged from a discharge port 3 of the tubular disperser, and acetone is removed by adopting a rotary evaporator (50 ℃, acetone removal is carried out under 1000 pa), and then the aqueous polyurethane dispersion emulsion is obtained.

Comparative example 1 of example 2

1. The preparation of the aqueous polyurethane prepolymer solution is the same as that of example 2;

2. preparing a water-based polyurethane dispersion coarse emulsion: and (2) selecting an IKA (IKA) online dispersing machine DR/DRS2000, dispersing the aqueous polyurethane prepolymer solution prepared in the step (1) in dispersing water, adding 5985 parts of prepolymer at one time, adding 2600 parts of dispersing water at one time, shearing at high speed to obtain aqueous polyurethane dispersion coarse emulsion, and removing acetone to obtain aqueous polyurethane dispersion emulsion. The parts added in the above reaction materials are parts by weight.

Comparative example 2 of example 2

1. The preparation of the aqueous polyurethane prepolymer solution is the same as that of example 2;

2. preparing a water-based polyurethane dispersion coarse emulsion: dispersing the aqueous polyurethane prepolymer solution prepared in the step 1 in dispersion water by adopting traditional intermittent dispersion, wherein 5985 parts of prepolymer is added at one time, 2600 parts of dispersion water is added into the prepolymer at one time within 10min, and the prepolymer is subjected to high-speed shearing dispersion by a dispersion disc to obtain aqueous polyurethane dispersion crude emulsion, and removing acetone to obtain the aqueous polyurethane dispersion emulsion. The parts added in the above reaction materials are parts by weight.

Example 3

1. Preparing a water-based polyurethane prepolymer solution: 421 parts of HDI, 145 parts of IPDI, 1500 parts of PNA2000, 61 parts of MPEG520 and 1 part of dibutyltin dilaurate catalyst were put into a tubular reactor, mixed and reacted at 75 ℃ for 3 hours, and then 98.7 parts of ethylenediamine, 33.5 parts of N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt and 825 parts of water were added and reacted at 45 ℃ for 20 minutes to obtain an aqueous polyurethane prepolymer solution.

2. Preparing a water-based polyurethane dispersion coarse emulsion: the continuous dispersion system III is adopted for dispersing the waterborne polyurethane prepolymer in the dispersion water, and specifically comprises the following steps:

10491 parts by weight of the aqueous polyurethane prepolymer solution prepared in the step 1 is added into a tubular disperser 1 from a feed inlet 2, and dispersed water is simultaneously added into the tubular disperser 1 from ten water inlets, and the concrete steps are as follows: 300 parts of dispersed water is metered by a metering pump and then is added from a first water inlet W1, 391 parts of dispersed water by weight is metered by a metering pump and then is added from a second water inlet W2, 400 parts of dispersed water by weight is metered by a metering pump and then is added from a third water inlet W3, 300 parts of dispersed water by weight is metered by a metering pump and then is added from a fourth water inlet W4, 260 parts of dispersed water by weight is metered by a metering pump and then is added from a fifth water inlet W5, 200 parts of dispersed water by weight is metered by a metering pump and then is added from a sixth water inlet W6, 200 parts of dispersed water by weight is metered by a metering pump and then is added from a seventh water inlet W7, 200 parts of dispersed water by weight is metered by a metering pump and then is added from an eighth water inlet W8, 200 parts of dispersed water by weight is metered by a metering pump and then is added from a ninth water inlet W9, 389 parts of dispersed water by weight is metered by a metering pump and then is added from a decimal water inlet W10.

The dispersing process conditions of the tubular disperser (1) comprise: the pressure drop of the inlet and the outlet is less than 0.2 Mpa; the dispersion rotating speed is 2100r/min, the reaction temperature is 31 ℃, and the reaction pressure is 0.8 Mpa; the flow rate of the mixture is 0.5m/min, the residence time of the mixture is 240 seconds, crude emulsion of the aqueous polyurethane dispersion is obtained, the crude emulsion is discharged from a discharge port 3 of the tubular disperser, and acetone is removed by a rotary evaporator (50 ℃, acetone removal is carried out under 1000 pa), and then aqueous polyurethane dispersion emulsion is obtained.

Comparative example 1 of example 3

1. The preparation of the aqueous polyurethane prepolymer solution is the same as that in example 3;

2. preparing a water-based polyurethane dispersion coarse emulsion: and (2) selecting an IKA (IKA) online dispersing machine DR/DRS2000, dispersing the aqueous polyurethane prepolymer solution prepared in the step (1) in dispersing water, wherein 10491 parts of prepolymer is added at one time, 2840 parts of dispersing water is added at one time, high-speed shearing is carried out to obtain aqueous polyurethane dispersion coarse emulsion, and acetone is removed to obtain aqueous polyurethane dispersion emulsion. The parts added in the above reaction materials are parts by weight.

Comparative example 2 of example 3

1. The preparation of the aqueous polyurethane prepolymer solution is the same as that of example 2;

2. preparing a water-based polyurethane dispersion coarse emulsion: dispersing the aqueous polyurethane prepolymer solution prepared in the step 1 in dispersion water by adopting traditional intermittent dispersion, wherein 10491 parts of prepolymer is added at one time, 2840 parts of dispersion water is added into the prepolymer at one time within 10min, and the prepolymer solution is subjected to high-speed shearing dispersion by a dispersion disc to obtain aqueous polyurethane dispersion coarse emulsion, and removing acetone to obtain aqueous polyurethane dispersion emulsion. The parts added in the above reaction materials are parts by weight.

The particle size and particle size distribution of the dispersions of the examples and the comparative examples, the test for (thermal) storage stability, and the test results for the application properties of the adhesives produced therewith are shown in Table 1.

TABLE 1 test results of dispersions and adhesives obtained therefrom in the examples and comparative examples

The comparison of the examples with the reference shows that: by using the continuous dispersion process of the present invention, the particle size of the aqueous polyurethane dispersion samples obtained in examples 1 to 3 is significantly smaller than that of the corresponding comparative samples 1 and 2, and the particle size distribution of the aqueous polyurethane dispersion samples obtained in examples 1 to 3 is also narrower than that of the corresponding comparative samples 1 and 2. In addition, the storage stability and the heat storage stability (good for more than 6 months, poor for 1 month and less) of the aqueous polyurethane dispersion samples obtained in examples 1 to 3 were all maintained at more than 6 months, and were significantly better than comparative sample 1, slightly better than or equal to comparative sample 2. The adhesive prepared from the aqueous polyurethane dispersion samples obtained in examples 1-3 has very good brushing property, and is significantly better than the corresponding comparative samples 1 and 2.

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (29)

1. A continuous dispersion system for preparing an aqueous polyurethane dispersion comprising:

the device comprises a tubular disperser (1), wherein the tubular disperser (1) is provided with a feed inlet (2) and a plurality of water inlets, and the plurality of water inlets are uniformly distributed along the axial direction of the tubular disperser (1);

the continuous dispersion system further comprises: the dispersing device comprises a motor (4), a middle shaft (5) positioned in the inner cavity of the tubular disperser (1) and a plurality of tooth row type dispersing disks (6) inserted in the middle shaft, wherein the middle shaft (5) is distributed along the axial direction of the tubular disperser, one end of the middle shaft is connected with the motor (4), and the other end of the middle shaft is fixed on the inner wall of the tubular disperser (1);

two inner partition plates (7) are arranged in the tubular disperser (1), the inner cavity of the tubular disperser is divided into three areas which are a premixing area, a phase transition area and a diluting area in sequence along the axial direction;

the number of the dentition type dispersion discs (6) arranged in the pre-mixing region is 2-11, the number of the dentition type dispersion discs (6) arranged in the phase transition region is 3-38, and the number of the dentition type dispersion discs (6) arranged in the dilution region is 1-5; the total number of tooth row type dispersion discs conforms to the following formula: 7< X + Y + Z < 50; x, Y, Z represents the number of tooth array type dispersion plates in the premixing area, the phase transition area and the dilution area in turn;

the dentition type dispersion plate (6) is a dentition type dispersion plate with an inner hole.

2. The continuous dispersing system according to claim 1, characterized in that the tubular disperser (1) has a length to diameter ratio of 5 to 105.

3. A continuous dispersion system according to claim 1, wherein said inner baffle (7) is provided with a plurality of irregular openings; and on each inner partition plate, the sum of the areas of the openings accounts for 15-75% of the total area of the inner partition plate.

4. Continuous dispersion system according to claim 1, characterised in that the distance of the two internal baffles (7) from the feed inlet (2) is 1/4 and 7/8 of the length of the tubular disperser chamber, respectively.

5. The continuous dispersing system of claim 1 wherein the sum of the areas of the internal bores on each of the serrated dispersing discs containing internal bores accounts for 5% to 87% of the total area of the serrated dispersing disc.

6. The continuous dispersing system of claim 5 wherein a plurality of regular and/or irregular bores are provided on the toothed dispersing disc, either uniformly or non-uniformly distributed.

7. A continuous dispersing system according to any one of claims 1-6 where there are also metering pumps on the tubular disperser (1) and where each of the water inlets is connected to one of the metering pumps.

8. The continuous dispersion system of claim 7, wherein the metering pump is a positive displacement pump.

9. A continuous dispersion process of an aqueous polyurethane dispersion, characterized in that the preparation of the aqueous polyurethane dispersion is carried out using the continuous dispersion system according to any one of claims 1 to 8, the continuous dispersion process comprising the steps of:

continuously adding the aqueous polyurethane prepolymer solution containing the solvent and the dispersing water into a tubular disperser (1), and fully mixing the mixture of the aqueous polyurethane prepolymer solution and the dispersing water under the action of a dentition type dispersing disc (6) to obtain the aqueous polyurethane dispersion containing the solvent.

10. The continuous dispersion process according to claim 9, wherein the aqueous polyurethane dispersion containing the solvent is obtained by removing the solvent.

11. The continuous dispersion process of claim 9, wherein the aqueous polyurethane prepolymer solution is prepared by an acetone method or a prepolymer method.

12. The continuous dispersion process of claim 11, wherein the aqueous polyurethane prepolymer solution is prepared by reacting polyisocyanate with oligomer polyol, a nonionic hydrophilic compound, a small molecule diol, a small molecule diamine, an ionic hydrophilic chain extender, a neutralizer and a solvent in a contact manner.

13. The continuous dispersion process according to claim 12, characterized in that the polyisocyanate is an aliphatic diisocyanate and/or an aromatic diisocyanate.

14. The continuous dispersion process according to claim 13, wherein the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate.

15. The continuous dispersion process of claim 12, wherein the oligomer polyol is selected from one or more of polyester diol, polyether diol, and polycarbonate diol.

16. The continuous dispersion process according to claim 15, wherein the polyester diol has a number average molecular weight of 200 to 5000, and is selected from one or more of polybutylene adipate diol, neopentyl glycol adipate diol, polyhexamethylene glycol adipate diol, polycaprolactone diol, polyhexamethylene glycol phthalate diol, and neopentyl glycol phthalate diol;

the number average molecular weight of the polyether diol is 200-5000, and the polyether diol is selected from one or more of polyoxypropylene diol, copolymerized diol of polyoxyethylene and polyoxypropylene and polytetrahydrofuran diol;

the polycarbonate diol has the number average molecular weight of 200-5000, and is prepared from carbonic diester and diol ester through ester exchange reaction.

17. The continuous dispersion process according to claim 12, wherein the non-ionic hydrophilic compound is a hydrophilic polyether compound containing mono-or di-functional groups reactive with isocyanate groups.

18. The continuous dispersion process according to claim 17, wherein the nonionically hydrophilic compounds are selected from the group consisting of compounds containing polyethoxy segments and having a number of ethylene oxide per molecule of 12 to 75, with a molar mass of 500-3000 g/mol.

19. The continuous dispersion process according to claim 12, wherein the small molecule diol is selected from one or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, neopentyl glycol and cyclohexanedimethanol.

20. The continuous dispersion process according to claim 12, wherein the small molecule diamine is selected from one or more of isophoronediamine, butanediamine, ethylenediamine, 1, 6-hexanediamine, piperazine, 1, 4-diaminocyclohexane, bis- (4-aminocyclohexyl) methane, adipic acid dihydrazide and hydrazine.

21. The continuous dispersion process according to claim 12, wherein the hydrophilic chain extender is selected from a dihydroxy compound containing hydrophilic groups, a diamino compound containing sulfonic acids or a diamino compound containing sulfonic acid salts.

22. The continuous dispersion process of claim 21, wherein the dihydroxy compound comprising a hydrophilic group is selected from one or more of dimethylol propionic acid, dimethylol butyric acid, dimethylol acetic acid, and dihydroxy succinic acid;

the diamino compound containing sulfonic acid or the diamino compound containing sulfonate is selected from one or more of N- (2-aminoethyl) -2-aminoethanesulfonic acid and alkali metal salts or ammonium salts thereof, N- (3-aminopropyl) -3-aminopropanesulfonic acid and alkali metal salts or ammonium salts thereof, and N- (2-aminoethyl) -3-aminopropanesulfonic acid and alkali metal salts or ammonium salts thereof.

23. The continuous dispersion process according to claim 12, wherein the neutralizing agent is selected from one or more of ammonia, ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol, morpholine, N-methylmorpholine, dimethylisopropylamine, N-methyldiethanolamine, triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine, sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide.

24. The continuous dispersion process according to claim 12, characterized in that the solvent is selected from butanone and/or acetone.

25. The continuous dispersion process according to any one of claims 9 to 24, wherein the aqueous polyurethane prepolymer solution is added into the tubular disperser (1) at a constant rate and quantity through the feed inlet (2); and simultaneously adding the dispersed water into the tubular disperser (1) through a plurality of uniformly distributed water inlets.

26. The continuous dispersion process according to claim 25, wherein the number of water inlets is ten, respectively a first water inlet (W1), a second water inlet (W2), a third water inlet (W3), a fourth water inlet (W4), a fifth water inlet (W5), a sixth water inlet (W6), a seventh water inlet (W7), an eighth water inlet (W8), a ninth water inlet (W9) and a tenth water inlet (W10), and the dispersed water is added simultaneously to the tubular disperser (1) by a metering pump connected to each water inlet in the following proportions:

the mass of the dispersed water added into the first water inlet (W1) accounts for 3-35% of the total added mass of the dispersed water, the mass of the dispersed water added into the second water inlet (W2) accounts for 3-35% of the total added mass of the dispersed water, the mass of the dispersed water added into the third water inlet (W3) accounts for 0-15% of the total added mass of the dispersed water, the mass of the dispersed water added into the fourth water inlet (W4) accounts for 0-15% of the total added mass of the dispersed water, the mass of the dispersed water added into the fifth water inlet (W5) accounts for 0-15% of the total added mass of the dispersed water, the mass of the dispersed water added into the sixth water inlet (W6) accounts for 0-15% of the total added mass of the dispersed water, the mass of the dispersed water added into the seventh water inlet (W7) accounts for 0-15% of the total added mass of the dispersed water, the mass of the dispersed water added into the eighth water inlet (W8) accounts for 5-30% of the total added mass of the dispersed water added into the ninth water inlet (W9), the mass of the dispersed water added into the decimal water gap (W10) accounts for 5-30% of the total added mass.

27. The continuous dispersion process according to any one of claims 9 to 24, 26, wherein the dispersion process conditions of the mixture within the tubular disperser (1) comprise: the dispersion rotating speed is 500-3000 r/min, the reaction temperature is 5-35 ℃, and the reaction pressure is 0.1-1 Mpa; the flow velocity of the mixture is 0.1-10 m/min, and the residence time of the mixture is 10-300 seconds; and/or

In the mixture, the mass ratio of the aqueous polyurethane prepolymer solution to the dispersed water is 1: 0.2-1: 3.

28. The continuous dispersion process according to claim 27, wherein the mass ratio of the aqueous polyurethane prepolymer solution to the dispersion water is 1:0.3 to 1: 1.1.

29. Use of the continuous dispersion process according to any one of claims 9 to 28 in the production of aqueous polyurethane by the acetone process, in the production of aqueous polyurethane by the prepolymer process, in the preparation of aqueous polyurethane acrylate dispersions and in the preparation of photocurable aqueous polyurethane acrylate dispersions.

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