CN107964104B - Solvent-free aqueous polyurethane dispersion, and preparation method and application thereof - Google Patents
Solvent-free aqueous polyurethane dispersion, and preparation method and application thereof Download PDFInfo
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- CN107964104B CN107964104B CN201711049515.0A CN201711049515A CN107964104B CN 107964104 B CN107964104 B CN 107964104B CN 201711049515 A CN201711049515 A CN 201711049515A CN 107964104 B CN107964104 B CN 107964104B
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Abstract
The invention provides a solvent-free aqueous polyurethane dispersion, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) respectively preheating polymer dihydric alcohol, diisocyanate, micromolecular dihydric alcohol, a low-melting-point double-end hydroxyl Y-shaped side chain hydrophilic chain extender and a catalyst, and inputting the preheated chain extender and the catalyst into a double-screw reactor for reaction to obtain a polyurethane melt; (2) injecting the water into a shear pump, and injecting the water with the surfactant into the shear pump for shearing and dispersing; (3) and cooling, depressurizing and stirring to obtain the solvent-free aqueous polyurethane dispersion. The invention solves the process problems of synthesis, dispersion, emulsification and the like of the high-viscosity aqueous polyurethane melt, and improves the production efficiency and the stability of the product batch; the method does not need to use a hydrophilic chain extender with higher price, and can be used for synthetic leather, adhesives, coatings, fabric coatings, finishing agents, base cloth bottom material resins, surface layer resins, bonding layer resins, middle layer resins or foaming layer resins.
Description
Technical Field
The invention relates to a method for producing aqueous polyurethane dispersions.
Background
The aqueous polyurethane dispersion takes water as a dispersion medium, only water is volatilized into the atmosphere in the using process, and no adverse effect is caused on the environment. Meanwhile, water is used as a dispersion medium, so that the aqueous polyurethane dispersion has the characteristics of no toxicity, no smell, no combustion, no explosion and safety. The aqueous polyurethane dispersion is widely applied as a green environment-friendly high polymer material, is also trending to replace oil-based polyurethane resin, and is widely applied to various fields such as synthetic leather, adhesives, building coatings and the like at present.
The development of waterborne polyurethane is extremely rapid since the industrialization of the last 60 years, but the production process is also a batch method and a semi-continuous method, which both involve prepolymerization in a reaction kettle. The biggest problem in the prepolymerization process is that the reaction vessel is generally difficult to handle high viscosity systems, and thus the prepolymerization process generally requires the addition of an organic solvent to reduce the viscosity of the polymerization system or to control the molecular weight of the prepolymer to an extremely low level. After the prepolymerization reaction is finished, transferring the materials to a dispersion kettle for neutralization and dispersion, and then removing the solvent in a desolventizing kettle. The aqueous polyurethane dispersion prepared by the process is often low in molecular weight, poor in performance and unstable in batch, or a large amount of solvents are needed in the production process, the solvents cannot participate in the polymerization process after being simply recovered and purified, so that the manufacturing cost is greatly increased, the requirements on equipment during emulsification are high, the large-scale production efficiency is low, and the time from feeding to discharging is generally 12-16 hours.
Many pioneers in the industry have developed a novel waterborne polyurethane preparation process, namely an ionomer process, also known as a pellet process. The core of the method is to prepare polyurethane ionomer particles by using a double-screw reactor, and then dissolve the ionomer in a solvent and remove the solvent to obtain the high-solid-content aqueous polyurethane dispersoid. The process adopts a bulk polymerization process without participation of a solvent and an emulsification process without participation of a reaction, so that the molecular weight of the aqueous dispersion can be greatly improved to improve and stabilize the performance, the solvent can be recycled without purification, and the production cost of the aqueous dispersion is greatly reduced. There are also a large number of workers at home and abroad who have or are still conducting a great deal of research work in this regard.
Patent CN 102336881A discloses that a double-screw extruder or a casting machine is adopted to prepare a waterborne polyurethane ionomer for a waterborne polyurethane adhesive by using polyester polyol, diisocyanate, a micromolecular chain extender and a hydrophilic monomer, and a good effect is achieved; patent CN 102633971A carries out simple prepolymerization in advance or dissolves DMPA with pyrrolidone (NMP) before the raw materials gets into the twin-screw reactor, realizes DMPA's accurate measurement, and the high temperature high pressure emulsification technique is in order to reduce the use amount of solvent in the production process, has improved waterborne polyurethane's production efficiency greatly and has reduced environmental pollution, but does not solve the operation difficulty problem that prepolymer viscosity under a small amount of solvent promotes the bring in the twinkling of an eye.
In patent CN103382253B, glycerin monomaleic anhydride ester and glycerin monobutyrate succinate are used to replace DMPA to realize the dissolution of hydrophilic chain extender in micromolecular dihydric alcohol and the accurate measurement, so that the waterborne polyurethane ionomer is smoothly and stably prepared, and after the hydrophilic chain extender is dissolved in acetone, neutralized by triethylamine and dispersed in water, the acetone is removed to obtain 30-60% waterborne polyurethane dispersoid.
The above works all adopt a double-screw technology to prepare polyurethane melt, and the aqueous polyurethane dispersion is prepared by processes of dissolving, salifying, dispersing, desolventizing and the like in sequence, and the solvent can be reused without purification.
The processes solve the defect of small molecular weight of the aqueous polyurethane dispersion and the simple recovery of the solvent, but do not relate to how to react the carbamido structure into the polyurethane, and the dependence on the solvent can not be got rid of in the dispersing and emulsifying processes, so that the aqueous polyurethane dispersion which is environment-friendly, has high performance and high added value can not be really prepared.
Disclosure of Invention
The invention aims to provide a continuous solvent-free aqueous polyurethane dispersion, a preparation method and application thereof, which overcome the defects in the prior art.
The method comprises the following steps:
(1) respectively preheating polymer dihydric alcohol, diisocyanate, micromolecular dihydric alcohol, a low-melting-point two-end hydroxyl Y-shaped side chain hydrophilic chain extender and a catalyst to 60-100 ℃, inputting the mixture into a mixer for dispersing and mixing, and inputting the mixture into a double-screw reactor for reaction to obtain a polyurethane melt with the number average molecular weight of 30000-200000;
the structure and the operation parameters of the double-screw reactor require that materials can have a great shearing and dispersing function in the axial direction and the radial direction of the screw, so that the metering deviation caused by the pulse of the metering equipment at different time can be overcome, and the inventor finds that the expected effect can be achieved by adopting a double-screw extruder with the L/D being more than or equal to 16 and less than or equal to 56 and the rotating speed being more than 200 and 300 rpm;
wherein: l represents the screw length and D represents the screw diameter;
in the double-screw reactor, the reaction temperature is divided into 7 sections, the first section is 80-130 ℃, the second section is 100-;
the polymer dihydric alcohol is one or a mixture of polyether dihydric alcohol, polyester dihydric alcohol and polycarbonate dihydric alcohol;
the polyether diol adopts polyether oligomers with 2-end hydroxyl and various structures with the number average molecular weight of 200-10000, and the polyether oligomers comprise but are not limited to: polytetrahydrofuran diol (PTMEG), polypropylene oxide diol (PPG), polyethylene oxide diol (PEG) and polypropylene oxide ethylene oxide copolymerized diol (PEPG) in any mixing ratio;
the polyester diol is an oligomer containing 2 terminal hydroxyl groups and a polyester structure, has a number average molecular weight of 200-4000, and comprises the following components in parts by weight: one or more of poly 1, 4-butylene adipate glycol (PBA), poly ethylene adipate glycol (PEA), poly propylene adipate glycol (PPA), poly 1, 6-hexanediol adipate glycol (PHA), poly neopentyl glycol adipate glycol (PNA), poly ethylene butylene adipate glycol (PEBA), poly ethylene propylene adipate glycol (PEPA), poly hexamethylene adipate neopentyl glycol ester glycol (PHNA), poly butylene glycol adipate hexanediol diol (PBHA), poly butylene glycol neopentyl glycol adipate glycol ester glycol (PBNA), and poly caprolactone glycol are mixed, and the mixing ratio is not limited;
the polycarbonate diol adopts an oligomer containing 2 terminal hydroxyl carbonic ester structures, has the number average molecular weight of 200-4000, is synthesized by exchanging carbonic diester with diol ester, and comprises the following components: one or more mixtures of poly (hexanediol carbonate), poly (pentanediol carbonate), poly (butylene carbonate), poly (propylene carbonate), and the like;
the diisocyanate is selected from one or a mixture of any combination of 4, 4-diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Xylylene Diisocyanate (XDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and hydrogenated 4, 4-diphenylmethane diisocyanate (HMDI);
the small molecular diol is selected from one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 8-octanediol, hydroquinone hydroxyethyl ether (HQEE), cyclohexyl dimethanol, 2-methyl-1, 3-propanediol and 2-methyl-1, 3-butanediol, and the mixing proportion is not limited;
the low-melting-point double-end hydroxyl Y-type side chain hydrophilic chain extender is selected from one or a mixture of 2-polyethylene glycol monomethyl ether-1, 4-butanediol with the number average molecular weight of 500-2000, and the mixing proportion is not limited;
the catalyst is one or a mixture of stannous octoate, dibutyltin dilaurate, organic zinc and organic bismuth;
(2) continuously injecting the obtained polyurethane melt into a shear pump, simultaneously injecting water with a surfactant into the shear pump, and shearing and dispersing at the high temperature of 120-200 ℃ and under the pressure of 0.2-1.5 Mpa;
the surfactant is one or a mixture of more of sodium hexadecyl sulfate, sodium dodecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate and triethanolamine lauryl sulfate;
(3) cooling the product obtained in the step (2) to 30-50 ℃, reducing the pressure, sending the product into a storage tank with a stirrer, and stirring for 5-15 min to obtain the solvent-free aqueous polyurethane dispersion with the solid content of 30-50% by weight;
the solvent-free aqueous polyurethane dispersion comprises the following components in percentage by mass:
preferably, the solvent-free aqueous polyurethane dispersion comprises the following components in percentage by mass:
the aqueous polyurethane dispersions prepared on the basis of the combined twin-screw reactor described above have a viscosity of 100 ℃ 2000mPas (20 ℃), preferably 200 ℃ 1000mPas (20 ℃).
The molecular weight of the aqueous polyurethane dispersion is between 30,000-200,000 so as to meet the requirements of high molecular weight, large cohesive energy, low modulus and high tensile strength required in practical application;
the aqueous polyurethane dispersion prepared by the method can be widely applied to various fields of synthetic leather, adhesives, coatings, fabric coatings, finishing agents and the like, and can be applied to the fields of base fabric primer resin, surface layer resin, bonding layer resin, middle layer resin, foaming layer resin and the like as synthetic leather resin.
The invention relates to a continuous solvent-free production process for preparing an aqueous polyurethane dispersion based on a double-screw reactor and a high-temperature shear pump, which is characterized in that raw materials of the aqueous polyurethane dispersion are polymerized into a high-molecular-weight polymer melt in the double-screw reactor within a short time, the melt is neutralized, dispersed and emulsified in the high-temperature and high-pressure shear pump, and then the aqueous polyurethane dispersion is obtained after cooling and pressure reduction. The process utilizes a double-screw process to realize high molecular weight, high cohesive energy and high performance of the waterborne polyurethane, utilizes high temperature to dissociate hydrogen bonds of the polyurethane to replace the traditional solvent to dissociate the hydrogen bonds so that molecular chains can slide, and utilizes a high-speed shear pump to replace a high-speed dispersion machine emulsification process so as to emulsify in a very short time, thereby further leading high-cohesive energy groups such as carbamido and the like to be implanted into a waterborne polyurethane molecular structure through a post-chain extension process, and realizing the advantages of high cohesive energy, heat resistance and the like. In a word, the process realizes the continuity, high performance and no solvent of the preparation of the aqueous polyurethane dispersion, greatly improves the performance and production efficiency of the aqueous polyurethane and realizes the perfect unification of the high performance and the low cost of the aqueous polyurethane.
Compared with the existing double-screw preparation process of the aqueous polyurethane dispersion and the traditional acetone prepolymer method aqueous process, the process can realize the following technical effects:
the double screw and the high-speed shear pump can solve the technical problems of synthesis, dispersion, emulsification and the like of the high-viscosity waterborne polyurethane melt, the process does not need the participation of a solvent, and the pure green environmental protection requirement of the waterborne polyurethane is really realized; by using a high-speed shear pump and adding an emulsifier if necessary, the nonionic polyurethane dispersion can be prepared, and the product quality and batch stability are good; the process is simple and efficient, only 30-60min is needed from feeding to output, the full-continuous automatic production requirement can be realized, and the production efficiency and the stability of product batches are improved; the process does not need to use a hydrophilic chain extender with higher price, reduces the production cost and improves the market competitiveness of the product.
Detailed Description
The invention is illustrated in detail by the following specific examples, but the scope of protection of the invention is not limited to these examples, but also includes non-essential formulation adjustments and process modifications according to the summary of the invention.
The basic properties of the polyurethane dispersions of the invention are characterized by the following test methods:
solid content determination: the clean surface dish was weighed out by an electronic balance to show a mass M1(ii) a Placing 2-3g of emulsion in a watch glass, and weighing the emulsion with the mass M2(ii) a Placing in a 120 ℃ blast oven 1Weighing the quality of the watch glass after hours, and continuously putting the watch glass into the oven until the weighed quality is constant, and recording M3。
Solid content: c ═ M3-M1)/(M2-M1)×100％
Tensile strength: refers to the stress at which the material undergoes maximum uniform plastic deformation. In the tensile test, the maximum tensile stress applied to the sample until the sample breaks is the tensile strength, and the maximum tensile stress can be calculated by dividing the maximum load by the sectional area of the sample.
Determination of tensile Strength: the polyurethane dispersion is uniformly coated on a polytetrafluoroethylene tray, dried at room temperature to form a film, dried in a blast oven at 120 ℃ for 1hr, placed in an oven at 50 ℃ for 8hr, placed in a test environment for 24hr, and tested for tensile strength at a tensile rate of 100 mm/min.
Elongation at break: the ratio of the displacement value of the sample at the time of tensile failure to the original length is expressed as a percentage (%).
100% modulus: it means the tensile strength at 100% elongation.
Example 1
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
polytetrahydrofuran diol (Mn ═ 2000), 2-polyethylene glycol monomethyl ether-1, 4-butanediol (Mn ═ 1000) and 2-methyl-1, 3-butanediol are mixed and heated to 80 ℃, a catalyst stannous octoate is added, 4, 4-diphenylmethane diisocyanate (MDI) is heated to 80 ℃, the two are respectively injected into a twin-screw reactor with the rotation speed of 250rpm, the L/D ═ 45, the temperature of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ and 210 ℃ through a gear metering pump and a flowmeter and react after passing through a mixing head, and the residence time is 0.5 min;
injecting into a shear pump with a melt gear pump at 150 deg.C and 1500rpm, shearing with a 0.5% wt sodium hexadecylsulfate solution at 150 deg.C and 0.5Mpa for 4 min;
cooling to 30 ℃ by a heat exchanger, reducing the pressure and the normal pressure, collecting the mixture in a stainless steel storage tank, fully collecting the mixture, and stirring for 15min to obtain the aqueous polyurethane dispersion with the solid content of 30.0 wt%.
The product properties were observed, there were no undissolved white flocs, the emulsion was stable and uniform, and the aqueous polyurethane dispersion did not precipitate white after standing for one month.
Example 2
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
mixing polytetrahydrofuran diol (Mn 4000), polyoxyethylene glycol (Mn 1000) and 1, 4-butanediol, heating to 60 ℃, adding a catalyst stannous octoate, heating Toluene Diisocyanate (TDI) to 60 ℃, and injecting the mixture into a double-screw reactor with the rotation speed of 200rpm, the L/D56, the temperature of 80 ℃, 100 ℃, 130 ℃, 140 ℃, 150 ℃, 170 ℃ and 215 ℃ respectively through a gear metering pump and a flowmeter, reacting for 2 min;
injecting into a shear pump with melt gear pump at 120 deg.C and rotation speed of 2500rpm, injecting into the shear pump with 120 deg.C, 0.2Mpa, and 2% wt sodium hexadecylsulfate solution, and shearing for 5 min;
cooling to 50 ℃ by a heat exchanger, reducing the pressure to normal pressure, collecting the mixture in a stainless steel storage tank, fully collecting the mixture, and stirring for 15min to obtain the aqueous polyurethane dispersion with the solid content of 37.0 wt%. The product properties were observed, there were no undissolved white flocs, the emulsion was stable and uniform, and the aqueous polyurethane dispersion did not precipitate white after standing for one month.
Example 3
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
mixing and heating 1, 4-butanediol adipate glycol (Mn ═ 4000), 2-polyethylene glycol monomethyl ether-1, 4-butanediol (Mn ═ 2000) and ethylene glycol to 100 ℃, adding a catalyst dibutyltin dilaurate, heating isophorone diisocyanate (IPDI) and hydrogenated 4, 4-diphenylmethane diisocyanate (HMDI) at a molar ratio of 1:2 to 100 ℃, respectively passing through a gear metering pump and a flowmeter, injecting the mixture into a twin-screw reactor with the rotating speed of 250rpm, the L/D ═ 50, the temperature of 100 ℃, 120 ℃, 130 ℃, 140 ℃, 170 ℃, 200 ℃ and 230 ℃ through a mixing head, and reacting for 1.5 min;
injecting into a shear pump with a melt gear pump at 200 deg.C and 1500rpm, and shearing with a shear pump at 200 deg.C, 1.5Mpa and 1% wt sodium dodecyl benzene sulfonate solution at a flow rate of 150kg/h for 3 min;
cooling to 30 ℃ by a heat exchanger, reducing the pressure to normal pressure, collecting the mixture in a stainless steel storage tank, fully collecting the mixture, and stirring for 10min to obtain the aqueous polyurethane dispersion with the solid content of 50.0 wt%. The product properties were observed, there were no undissolved white flocs, the emulsion was stable and uniform, and the aqueous polyurethane dispersion did not precipitate white after standing for one month.
Example 4
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
mixing and heating polyoxypropylene ethylene oxide copolymerized dihydric alcohol (Mn is 2000), polyethylene glycol adipate diol (Mn is 2000), 2-polyethylene glycol monomethyl ether-1, 4-butanediol (Mn is 500) and 1, 4-butanediol to 90 ℃, adding a catalyst dibutyltin dilaurate, and heating 4, 4-diphenylmethane diisocyanate (MDI) to 90 ℃, wherein the two are respectively heated to 90 ℃, and the two are respectively injected into a double-screw reactor with the rotation speed of 300rpm, the L/D is 45, the temperature of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ and 210 ℃ for reaction through a gear metering pump and a flow meter after passing through a mixing head, and the residence time is 3 min;
injecting into a shear pump with melt gear pump at 180 deg.C and 1500rpm, and injecting into the shear pump with triethanolamine dodecyl benzene sulfonate solution with temperature of 180 deg.C, pressure of 1.3Mpa and concentration of 1.5% by weight, and shearing for 3 min;
cooling to 40 ℃ by a heat exchanger, reducing the pressure to normal pressure, collecting the mixture in a stainless steel storage tank, fully collecting the mixture, and stirring for 5min to obtain the aqueous polyurethane dispersion with the solid content of 40.0 wt%. The product properties were observed, there were no undissolved white flocs, the emulsion was stable and uniform, and the aqueous polyurethane dispersion did not precipitate white after standing for one month.
Example 5
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
mixing and heating polyethylene carbonate glycol (Mn ═ 2000), 2-polyethylene glycol monomethyl ether-1, 4-butanediol (Mn ═ 1000) and neopentyl glycol to 100 ℃, adding a catalyst stannous octoate, heating 4, 4-diphenylmethane diisocyanate (MDI) to 100 ℃, and reacting the two by a gear metering pump and a flowmeter respectively, and injecting into a double-screw reactor with the rotation speed of 300rpm, the L/D ═ 16, the temperature of 130 ℃, 140 ℃, 150 ℃, 205 ℃ respectively after head closing, wherein the retention time is 2.5 min;
injecting into a shear pump with a melt gear pump at 150 deg.C and 2000rpm, injecting triethanolamine lauryl sulfate and sodium dodecylbenzenesulfonate solution at 150 deg.C, 0.5Mpa and 2% wt at a molar ratio of 1:1, and shearing for 4 min;
cooling to 30 ℃ by a heat exchanger, reducing the pressure to normal pressure, collecting the mixture in a stainless steel storage tank, fully collecting the mixture, and stirring for 15min to obtain the aqueous polyurethane dispersion with the solid content of 45.6 wt%. The product properties were observed, there were no undissolved white flocs, the emulsion was stable and uniform, and the aqueous polyurethane dispersion did not precipitate white after standing for one month.
Example 6
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
mixing polyoxyethylene glycol (Mn ═ 2000), 2-polyethylene glycol monomethyl ether-1, 4-butanediol (Mn ═ 1000) and neopentyl glycol, heating to 80 ℃, adding catalyst stannous octoate, heating Toluene Diisocyanate (TDI) to 80 ℃, allowing the two to pass through a gear metering pump and a flow meter respectively, injecting into a double-screw reactor with the rotation speed of 300rpm, the L/D ═ 30, the temperature of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 170 ℃ and 215 ℃ respectively, and allowing the mixture to react for 1 min;
injecting into a shear pump with a melt gear pump at 120 deg.C and rotation speed of 2500rpm, and injecting into the shear pump with a solution of 4% wt of sodium dodecylbenzenesulfonate at 120 deg.C for 5 min;
cooling to 40 ℃ by a heat exchanger, reducing the pressure to normal pressure, collecting the mixture in a stainless steel storage tank, fully collecting the mixture, and stirring for 15min to obtain the aqueous polyurethane dispersion with the solid content of 37.9 wt%. The product properties were observed, there were no undissolved white flocs, the emulsion was stable and uniform, and the aqueous polyurethane dispersion did not precipitate white after standing for one month.
Comparative example 1
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
polytetrahydrofuran diol (Mn ═ 2000), 2-polyethylene glycol monomethyl ether-1, 4-butanediol (Mn ═ 1000) and 2-methyl-1, 3-butanediol are mixed and heated to 80 ℃, a catalyst stannous octoate is added, 4, 4-diphenylmethane diisocyanate (MDI) is heated to 80 ℃, the two are respectively injected into a twin-screw reactor with the rotation speed of 250rpm, the L/D ═ 70, the temperature of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ and 210 ℃ through a mixing head and react by a gear metering pump and a flowmeter, and the residence time is 1 min;
injecting into a shear pump with melt gear pump at 150 deg.C and 1500rpm, and injecting into the shear pump with 150 deg.C, 0.5Mpa and 0.5% wt sodium hexadecylsulfate solution, and shearing for 4 min;
cooling to 30 deg.C with heat exchanger, reducing pressure and normal pressure, collecting in stainless steel storage tank, collecting, and stirring for 15 min; thus obtaining the aqueous polyurethane dispersion with the solid content of 30.0 wt%.
The product properties were observed to reveal a large amount of undissolved white floc, and a stable and uniform emulsion could not be obtained.
Comparative example 2
The formula is as follows: (percent by mass)
The preparation method comprises the following steps:
mixing polyoxyethylene glycol (Mn ═ 2000), 2-polyethylene glycol monomethyl ether-1, 4-butanediol (Mn ═ 1000) and neopentyl glycol until the mixture is heated to 80 ℃, adding catalyst stannous octoate, heating Toluene Diisocyanate (TDI) to 80 ℃, and injecting the mixture into a double-screw reactor with the rotation speed of 300rpm, the L/D ═ 10, the temperatures of 120 ℃, 130 ℃, 140 ℃, 150 ℃, 170 ℃ and 215 ℃ respectively through a mixing head and a flow meter for reaction, wherein the residence time is 3 min;
injecting into a shear pump with a melt gear pump at 120 deg.C and rotation speed of 2500rpm, and shearing with a shear pump at 120 deg.C and 4% wt of sodium dodecyl benzene sulfonate solution at 220kg/h flow rate for 5 min;
cooling to 40 ℃ by a heat exchanger, reducing the pressure to normal pressure, collecting the mixture in a stainless steel storage tank, fully collecting the mixture, and stirring for 15min to obtain the aqueous polyurethane dispersion with the solid content of 37.9 wt%.
The product had poor stability and after standing for two days, a large amount of white precipitate appeared.
The physical properties of the aqueous polyurethane dispersions obtained in examples 1 to 6 were as follows:
| examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Solid content | 30.0％wt | 37％wt | 50.0％wt | 40.0％wt | 45.6％wt | 37.9％wt |
| Emulsion viscosity (20 ℃ C.) | 200cp | 350cp | 840cp | 530cp | 480cp | 320cp |
| 100% modulus | 1.2 | 2.1 | 3.4 | 1.5 | 1.7 | 1.1 |
| Tensile strength (Mpa) | 24 | 37 | 46 | 29 | 26 | 22 |
| Elongation at break% | 900 | 840 | 730 | 950 | 800 | 970 |
The detection results of the embodiment and the comparative example show that the double-screw reactor of the invention uses special length-diameter ratio, proper temperature and time, so that the occurrence of side reactions is reduced as much as possible while the raw materials are completely reacted, and the prepared WTPUT emulsion has good storage stability and excellent performance, can be widely applied to various fields of synthetic leather, adhesives, coatings, fabric coatings, finishing agents and the like, particularly used as synthetic leather resin, and can be applied to the fields of base fabric backing resin, surface layer resin, bonding layer resin, middle layer resin, foaming layer resin and the like.
Claims (3)
1. The preparation method of the solvent-free nonionic aqueous polyurethane dispersion with the molecular weight of 30000-200000 is characterized by comprising the following steps:
(1) respectively preheating polymer dihydric alcohol, diisocyanate, micromolecular dihydric alcohol, a low-melting-point double-end hydroxyl Y-shaped side chain hydrophilic chain extender and a catalyst, inputting the preheated materials into a mixer for dispersing and mixing, and inputting the mixture into a double-screw reactor for reaction to obtain a polyurethane melt;
(2) continuously injecting the obtained polyurethane melt into a shear pump, and simultaneously injecting water with a surfactant into the shear pump for shearing and dispersing;
(3) cooling and depressurizing the product obtained in the step (2), and stirring to obtain the solvent-free nonionic aqueous polyurethane dispersion;
in the step (1), the double-screw reactor adopts a double-screw extruder with L/D being more than or equal to 16 and less than or equal to 56 and the rotating speed being 200-300rpm, wherein: l represents the screw length and D represents the screw diameter; in the double-screw reactor, the reaction temperature is divided into 7 sections, the first section is 80-130 ℃, the second section is 100-;
the solvent-free nonionic aqueous polyurethane dispersion comprises the following components in percentage by mass:
the polymer diol is selected from one or more of polytetrahydrofuran diol with the number average molecular weight of 2000, polytetrahydrofuran diol with the number average molecular weight of 4000, polyethylene oxide diol with the number average molecular weight of 1000, polyethylene oxide diol with the number average molecular weight of 2000, polypropylene oxide ethylene copolymer diol with the number average molecular weight of 2000, polyethylene adipate diol with the number average molecular weight of 2000, 1, 4-butanediol adipate diol with the number average molecular weight of 4000 and polyethylene carbonate diol with the number average molecular weight of 2000;
the diisocyanate is selected from more than one of 4, 4-diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI);
the micromolecular dihydric alcohol is selected from ethylene glycol, 1, 4-butanediol, neopentyl glycol or 2-methyl-1, 3-butanediol;
the low-melting-point double-end hydroxyl Y-type side chain hydrophilic chain extender is selected from more than one of 2-polyethylene glycol monomethyl ether-1, 4-butanediol with the number average molecular weight of 500-2000-;
the catalyst is stannous octoate or dibutyltin dilaurate;
the surfactant is one or two selected from sodium hexadecyl sulfate, sodium dodecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate and triethanolamine lauryl sulfate.
2. The solvent-free nonionic aqueous polyurethane dispersion prepared by the preparation method according to claim 1.
3. The use of the solventless nonionic aqueous polyurethane dispersion according to claim 2 for synthetic leather, adhesives, coatings, textile coatings, finishes, base fabric primer resins, top layer resins, tie layer resins, middle layer resins or foam layer resins.
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| WO2013176257A1 (en) * | 2012-05-25 | 2013-11-28 | トーヨーポリマー株式会社 | Aqueous polyurethane dispersing element, film-molded body obtained therefrom, and glove |
| CN107099015A (en) * | 2017-03-24 | 2017-08-29 | 广东科茂林产化工股份有限公司 | A kind of modified aqueous polyurethane dispersoid and preparation method thereof |
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| WO2013176257A1 (en) * | 2012-05-25 | 2013-11-28 | トーヨーポリマー株式会社 | Aqueous polyurethane dispersing element, film-molded body obtained therefrom, and glove |
| CN107099015A (en) * | 2017-03-24 | 2017-08-29 | 广东科茂林产化工股份有限公司 | A kind of modified aqueous polyurethane dispersoid and preparation method thereof |
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