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CN113024757B - Method for preparing waterborne polyurethane through prepolymerization-emulsification full-continuous method - Google Patents

Method for preparing waterborne polyurethane through prepolymerization-emulsification full-continuous method Download PDF

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Publication number
CN113024757B
CN113024757B CN202110233082.4A CN202110233082A CN113024757B CN 113024757 B CN113024757 B CN 113024757B CN 202110233082 A CN202110233082 A CN 202110233082A CN 113024757 B CN113024757 B CN 113024757B
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chain extender
parts
reaction
waterborne polyurethane
emulsification
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CN113024757A (en
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陈意
周帅
范浩军
颜俊
李成祥
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Sichuan University
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Sichuan University
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Priority to PCT/CN2021/095919 priority patent/WO2022183604A1/en
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Abstract

The invention discloses a process method for preparing waterborne polyurethane by prepolymerization-emulsification in a full-continuous way. The method takes a sonochemistry-enhanced double-screw extruder as a pre-polymerization and neutralization reactor of the waterborne polyurethane, takes a static mixer and a tubular emulsifier as a pre-polymer emulsifying device, carries out pre-polymerization and emulsification fully continuously, has high production efficiency, low cost and stable product quality, and is particularly suitable for the production of the waterborne polyurethane with high solid content. More importantly, a special ultrasonic generator is additionally arranged in a specific area of the double-screw extruder to perform sonochemical treatment on the prepolymerization intermediate, so that the material reaction activity can be remarkably improved, the prepolymerization reaction can be quickly completed at the low temperature of 70-80 ℃ in the later stage, the production process is energy-saving and environment-friendly, the occurrence of side reactions such as branching, crosslinking and degradation caused by high temperature in the later stage is avoided, and the obtained waterborne polyurethane has a controllable structure and stable quality. The process method does not use any organic solvent, has no selectivity to raw materials, and is suitable for the synthesis of any type of waterborne polyurethane.

Description

Method for preparing waterborne polyurethane through prepolymerization-emulsification full-continuous method
Technical Field
The invention relates to a method for preparing waterborne polyurethane by prepolymerization-emulsification in a full-continuous way, belonging to the field of high polymer materials.
Background
Waterborne polyurethanes were introduced in the last 60 th century and are new polyurethane systems using water as the dispersing medium instead of organic solvents. Compared with the traditional solvent type polyurethane, the waterborne polyurethane only volatilizes water and enters the atmosphere in the using process, is environment-friendly and meets the requirements of modern green chemical engineering processes; meanwhile, as the dispersion medium is water, the waterborne polyurethane has the characteristics of no toxicity, no flammability, no explosion and the like, can replace the traditional solvent type polyurethane, is widely applied to the fields of leather, synthetic leather, biomedical treatment, furniture, automobiles, aerospace and the like, and belongs to a new material which is mainly developed by China.
At present, the most common production process of the waterborne polyurethane is batch production, namely, a polyurethane prepolymer with a main chain containing hydrophilic groups is synthesized in a prepolymerization reaction kettle, and then the materials are transferred to a dispersion kettle for neutralization and are added with water for emulsification. The production process mainly has the following disadvantages: (1) the reaction time is long (6-8 hours), the production efficiency is low, and the production cost is high; (2) the production excessively depends on manual work, and the automation degree is low; (3) the product quality is unstable, and the difference among batches is large; (4) in order to facilitate emulsification, a low-boiling-point organic solvent is added into the prepolymer to reduce viscosity, and the solvent is removed by reduced pressure distillation after emulsification, so that energy consumption is increased and resources are wasted; (5) the low solids content of the product results in high drying and shipping costs.
The continuous production can solve the bottleneck problem existing in the traditional intermittent production. Patents CN202011253943.7, CN201310255840.8, CN201711045576.x, CN201711049518.4 and CN201210116805.3 all adopt a twin-screw extruder as a reactor for synthesizing waterborne polyurethane, and can realize continuous production of waterborne polyurethane. Since the twin-screw extruder is characterized by high production efficiency and short action time, the above patent can only shorten the reaction time by increasing the reaction temperature (which is even higher than 200 ℃). However, the temperature of the polyurethane reaction is generally in the range of 70-90 ℃, especially in the later stage of the reaction, if the temperature exceeds 90 ℃, side reactions such as branching and crosslinking can be initiated, the raw material ratio is damaged, the product structure is out of control, the emulsification is difficult, and the product quality is also influenced.
Disclosure of Invention
The invention provides a method for preparing waterborne polyurethane by prepolymerization-emulsification in a full-continuous way in order to overcome the defects and shortcomings of the prior art, which is characterized in that the method comprises the following process steps and conditions, and the parts of the used materials are the parts by weight:
(1) uniformly mixing 50-180 parts of diisocyanate, 80-300 parts of dihydric alcohol, 1-10 parts of micromolecular chain extender, 5-20 parts of hydrophilic chain extender and 0.055-0.24 part of catalyst, preheating to 150 ℃ and continuously injecting into a first-stage double-screw reactor, wherein the reaction temperature is controlled at 150 ℃ and the reaction time is 2-4 min;
(2) after the first-stage reaction is finished, the material enters a second-stage ultrasonic treatment area, and the ultrasonic intensity is 200-ion 300W/cm2The frequency is 25-30kHz, the reaction temperature is controlled at 70-80 ℃, and the reaction time is 3-6 min;
(3) after the second stage reaction, the material enters a third stage double-screw reactor, the reaction temperature is controlled at 70-80 ℃, and the reaction time is 5-8 min;
(4) after the third-stage reaction is finished, feeding the material and 0-15 parts of neutralizer into a fourth-stage double-screw reactor, controlling the reaction temperature at 30-40 ℃ and reacting for 1-2min to obtain a neutralized product;
(5) injecting the neutralization product, 300 portions of deionized water and 1100 portions of the post chain extender and 0-3 portions of the post chain extender into the fifth-stage static mixer for pre-emulsification;
(6) after pre-emulsification is finished, the material enters a sixth section of tubular emulsifier, the circulating flow rate is 200-400r/min, the circulating frequency is 30-50 times, the emulsifying time is 20-40min, and the waterborne polyurethane is obtained after emulsification;
in the steps (1), (3) and (4), the ratio of the length L to the diameter D of the screw of the double-screw reactor is more than or equal to 15 and less than or equal to 30, and the rotating speed is 200-;
the diisocyanate in the step (1) is one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate and hexamethylene diisocyanate;
in the step (1), the dihydric alcohol is one or more of polybutylene adipate glycol, polyethylene adipate glycol, polypropylene glycol, polyethylene carbonate glycol and polypropylene carbonate glycol with the number average molecular weight of 500-8000;
in the step (1), the micromolecular chain extender is one or more of 1, 4-butanediol, 1, 3-propanediol, glycol, ethylenediamine and 1, 4-butanediamine;
the hydrophilic chain extender in the step (1) is one or more of dimethylolpropionic acid, dimethylolbutyric acid, methyldiethanolamine, ethylenediamine ethanesulfonic acid sodium salt and 1, 4-butanediol-2-sulfonic acid sodium salt;
the catalyst in the step (1) is one or more of dibutyltin dilaurate, bismuth isooctanoate, bismuth laurate and bismuth neodecanoate;
the neutralizing agent in the step (4) is a compound for neutralizing hydrophilic groups in the hydrophilic chain extender into ionic groups; for a hydrophilic chain extender of dimethylolpropionic acid and dimethylolbutyric acid, the neutralizer is one or more of triethylamine and dimethylethanolamine, for a hydrophilic chain extender of methyldiethanolamine, the neutralizer is one or more of formic acid and acetic acid, and for a hydrophilic chain extender of ethylenediamine ethanesulfonic acid sodium salt and 1, 4-butanediol-2-sulfonic acid sodium salt, the neutralizer is not needed;
in the step (5), the rear chain extender is one or more of ethylenediamine, hexamethylenediamine, hydrazine hydrate and p-phenylenediamine.
The principle of the method is as follows:
after a great deal of experiments, the invention discovers that after the pre-reaction is carried out for 2-4min under the condition (100-150 ℃) in the step (1) of the claim, the reaction degree of the waterborne polyurethane is about 15-20%, and the temperature is higher in this stage, but the side reaction is less. After the stage, if the material is subjected to the ultrasonic treatment in the step (2), under the cavitation action of the ultrasonic wave, the reactivity of the isocyanate groups in the material with the hydroxyl groups and the amino groups is greatly improved; the whole reaction can be completed only by reacting in a twin-screw reactor at 70-80 ℃ for 5-8min in the later period. Because the later reaction temperature is the same as that of the traditional intermittent process, the problems of increased byproducts and out-of-control product structure caused by high temperature in the later period are avoided.
It should be noted that the timing and conditions of the addition of the sonication zone must be strictly limited. Experiments show that if the second ultrasonic treatment is too early, the reactivity of the material is not improved enough, and the reaction cannot be pushed to 100% in a short time at the low temperature of 70-80 ℃ in the third section; if the ultrasonic treatment of the second stage is too late, the reactivity of the material is excessively improved, a large amount of side reactions occur in the third stage, the viscosity of the product is suddenly increased, and even the normal emulsification cannot be realized. Meanwhile, the time, intensity, frequency and temperature of the second ultrasonic treatment are strictly limited to the conditions in the step (2) of the claims, and the reaction activity of the material is improved insufficiently or excessively.
Compared with the prior art, the method has the beneficial effects that:
(1) an ultrasonic treatment area is added between the first and third sections of double-screw reactors, the time, the intensity, the temperature and the frequency of ultrasonic treatment are strictly limited, the reaction activity of the waterborne polyurethane prepolymer intermediate can be obviously improved, the reaction later stage can be carried out at the low temperature of 70-80 ℃, meanwhile, the reaction time can not be greatly prolonged, the high efficiency of the double-screw extrusion reaction is kept, the production method is energy-saving and environment-friendly, the reaction side reaction is less, and the product structure is controllable;
(2) the whole prepolymerization and emulsification processes are carried out in a full-continuous manner, the production efficiency is high, the automation degree is high, the production cost is low, the product quality is stable, and the method is particularly suitable for producing the high-solid-content waterborne polyurethane;
(3) the process method does not use any organic solvent, has no selectivity to raw materials, and is suitable for synthesizing any type of waterborne polyurethane.
Detailed Description
The invention is described in detail below with reference to examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and many insubstantial modifications and variations of the invention can be made by an engineer skilled in the art based on the teachings of the invention.
Example 1:
the formula is as follows: (parts by weight)
80 parts of polymer diol: polyethylene carbonate diol (Mn = 3000)
50 parts of diisocyanate: isophorone diisocyanate
2 parts of a small-molecule chain extender: 1, 3-propanediol
5 parts of a hydrophilic chain extender: methyldiethanolamine
0.055 part of catalyst: dibutyl tin dilaurate
300 parts of deionized water
1.93 parts of a neutralizing agent: formic acid
2 parts of a post-chain extender: ethylene diamine
The preparation method comprises the following steps:
(1) uniformly mixing 50 parts of isophorone diisocyanate, 80 parts of polyethylene carbonate glycol (Mn = 3000), 2 parts of a small molecular chain extender (1, 3-propylene glycol), 5 parts of a hydrophilic chain extender (methyldiethanolamine) and 0.055 part of a catalyst (dibutyltin dilaurate), preheating to 100 ℃, continuously injecting into a first section of double-screw reactor, controlling the reaction temperature at 120 ℃, and reacting for 3 min;
(2) after the first stage reaction, the material enters a second ultrasonic treatment area with the ultrasonic intensity of 200W/cm2The frequency is 25kHz, the reaction temperature is controlled at 70 ℃, and the reaction time is 6 min;
(3) after the second stage reaction, the material enters a third stage double-screw reactor, the reaction temperature is controlled at 70 ℃, and the reaction time is 8 min;
(4) after the third stage of reaction is finished, the materials and 1.93 parts of neutralizer (formic acid) enter a fourth stage of double-screw reactor, the reaction temperature is controlled at 30 ℃, and the reaction time is 2min, so that a neutralized product is obtained;
(5) injecting the neutralized product, 300 parts of deionized water and 2 parts of post chain extender (ethylene diamine) into a fifth-stage static mixer at the same time for pre-emulsification;
(6) after pre-emulsification is finished, feeding the materials into a sixth section of tubular emulsifier, wherein the circulating flow rate is 200r/min, the circulating times are 35 times, and the emulsifying time is 40min, and emulsifying to obtain waterborne polyurethane;
the ratio of the length L of the screw rod of the double-screw reactor to the diameter D of the screw rod of the double-screw reactor in the steps (1), (3) and (4) is L/D =20, and the rotating speed is 200 rmp.
Example 2:
the formula is as follows: (parts by weight)
200 parts of polymer diol: polyethylene carbonate diol (Mn = 2000)
100 parts of diisocyanate: toluene diisocyanate
6 parts of a micromolecular chain extender: 1, 4-butanediol
15 parts of a hydrophilic chain extender: dimethylolpropionic acid
0.15 part of catalyst: bismuth Isooctanoate
400 parts of deionized water
10 parts of a neutralizing agent: dimethylethanolamine
2.5 parts of a post-chain extender: hydrazine hydrate
The preparation method comprises the following steps:
(1) uniformly mixing 100 parts of toluene diisocyanate, 200 parts of poly (ethylene carbonate) diol (Mn = 2000), 6 parts of micromolecular chain extender (1, 4-butanediol), 15 parts of hydrophilic chain extender (dimethylolpropionic acid) and 0.15 part of catalyst (bismuth isooctanoate), preheating to 120 ℃, continuously injecting into a first section of double-screw reactor, controlling the reaction temperature at 130 ℃, and reacting for 3 min;
(2) after the first stage reaction, the material enters a second ultrasonic treatment area, and the ultrasonic intensity is 300W/cm2The frequency is 30kHz, the reaction temperature is controlled at 72 ℃, and the reaction time is 4 min;
(3) after the second stage reaction, the material enters a third stage double-screw reactor, the reaction temperature is controlled at 75 ℃, and the reaction time is 6 min;
(4) after the third-stage reaction is finished, the material and 10 parts of neutralizer (dimethylethanolamine) enter a fourth-stage double-screw reactor, the reaction temperature is controlled at 35 ℃, and the reaction time is 1.5min, so that a neutralized product is obtained;
(5) injecting a neutralization product, 400 parts of deionized water and 2.5 parts of a post chain extender (hydrazine hydrate) into a fifth-stage static mixer at the same time for pre-emulsification;
(6) after pre-emulsification is finished, feeding the materials into a sixth section of tubular emulsifier, wherein the circulating flow rate is 300r/min, the circulating times are 40 times, and the emulsifying time is 30min, and emulsifying to obtain waterborne polyurethane;
the ratio of the length L of the screw rod of the double-screw reactor to the diameter D of the screw rod of the double-screw reactor in the steps (1), (3) and (4) is L/D =25, and the rotating speed is 250 rmp.
Example 3:
the formula is as follows: (parts by weight)
300 parts of polymer diol: polyethylene glycol (Mn = 2000)
180 parts of diisocyanate: hexamethylene diisocyanate
8 parts of a small-molecule chain extender: ethylene glycol
20 parts of a hydrophilic chain extender: 1, 4-butanediol-2-sulfonic acid sodium salt
0.22 part of catalyst: lauric acid bismuth
400 parts of deionized water
2 parts of a post-chain extender: p-phenylenediamine
(1) Uniformly mixing 180 parts of hexamethylene diisocyanate, 300 parts of polyethylene glycol (Mn = 2000), 8 parts of micromolecular chain extender (ethylene glycol), 20 parts of hydrophilic chain extender (1, 4-butanediol-2-sodium sulfonate) and 0.22 part of catalyst (bismuth laurate), preheating to 120 ℃, continuously injecting into a first section of double-screw reactor, controlling the reaction temperature at 140 ℃, and reacting for 2 min;
(2) after the first stage reaction, the material enters a second ultrasonic treatment area, and the ultrasonic intensity is 250W/cm2The frequency is 25kHz, the reaction temperature is controlled at 78 ℃, and the reaction time is 3 min;
(3) after the second stage reaction, the material enters a third stage double-screw reactor, the reaction temperature is controlled at 80 ℃, and the reaction time is 5 min;
(4) after the third-stage reaction is finished, directly feeding the materials into a fourth-stage double-screw reactor, controlling the reaction temperature at 40 ℃ and the reaction time for 1min to obtain a reaction product;
(5) injecting the reaction product, 400 parts of deionized water and 2 parts of a rear chain extender (p-phenylenediamine) into a fifth-stage static mixer at the same time for pre-emulsification;
(6) after pre-emulsification is finished, feeding the materials into a sixth section of tubular emulsifier, wherein the circulating flow rate is 400r/min, the circulating times are 40 times, and the emulsifying time is 35min, and emulsifying to obtain waterborne polyurethane;
the ratio of the length L of the screw rod of the double-screw reactor to the diameter D in the steps (1), (3) and (4) is L/D =20, and the rotating speed is 300 rmp.
Examples 1 to 3 the resulting aqueous polyurethane compositionsThe properties were as follows:
examples Example 1 Example 2 Example 3
Solid content 31% 45% 56%
Emulsion viscosity (20 ℃ C.) 245cP 420cP 580cP
Modulus at 100% elongation 1.3 1.9 4.2
Tensile Strength (MPa) 9 26 38
Elongation at break 840 930 1150

Claims (1)

1. A method for preparing waterborne polyurethane by prepolymerization-emulsification full-continuous is characterized in that the method comprises the following process steps and conditions, and the parts of the used materials are the parts by weight:
(1) uniformly mixing 50-180 parts of diisocyanate, 80-300 parts of dihydric alcohol, 1-10 parts of micromolecular chain extender, 5-20 parts of hydrophilic chain extender and 0.055-0.24 part of catalyst, preheating to 150 ℃ and continuously injecting into a first-stage double-screw reactor, wherein the reaction temperature is controlled at 150 ℃ and the reaction time is 2-4 min;
(2) after the first-stage reaction is finished, the material enters a second-stage ultrasonic treatment area, and the ultrasonic intensity is 200-ion 300W/cm2The frequency is 25-30kHz, the reaction temperature is controlled at 70-80 ℃, and the reaction time is 3 DEG-6min；
(3) After the second stage reaction, the material enters a third stage double-screw reactor, the reaction temperature is controlled at 70-80 ℃, and the reaction time is 5-8 min;
(4) after the third-stage reaction is finished, feeding the material and 0-15 parts of neutralizer into a fourth-stage double-screw reactor, controlling the reaction temperature at 30-40 ℃ and reacting for 1-2min to obtain a neutralized product;
(5) injecting the neutralization product, 300 portions of deionized water and 1100 portions of the post chain extender and 0-3 portions of the post chain extender into the fifth-stage static mixer for pre-emulsification;
(6) after pre-emulsification is finished, the material enters a sixth section of tubular emulsifier, the circulating flow rate is 200-400r/min, the circulating frequency is 30-50 times, the emulsifying time is 20-40min, and the waterborne polyurethane is obtained after emulsification;
in the steps (1), (3) and (4), the ratio of the length L to the diameter D of the screw of the double-screw reactor is more than or equal to 15 and less than or equal to 30, and the rotating speed is 200-;
the diisocyanate in the step (1) is one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate and hexamethylene diisocyanate;
in the step (1), the dihydric alcohol is one or more of polybutylene adipate glycol, polyethylene adipate glycol, polypropylene glycol, polyethylene carbonate glycol and polypropylene carbonate glycol with the number average molecular weight of 500-8000;
in the step (1), the micromolecular chain extender is one or more of 1, 4-butanediol, 1, 3-propanediol, glycol, ethylenediamine and 1, 4-butanediamine;
the hydrophilic chain extender in the step (1) is one or more of dimethylolpropionic acid, dimethylolbutyric acid, methyldiethanolamine, ethylenediamine ethanesulfonic acid sodium salt and 1, 4-butanediol-2-sulfonic acid sodium salt;
the catalyst in the step (1) is one or more of dibutyltin dilaurate, bismuth isooctanoate, bismuth laurate and bismuth neodecanoate;
the neutralizing agent in the step (4) is a compound for neutralizing hydrophilic groups in the hydrophilic chain extender into ionic groups; for a hydrophilic chain extender of dimethylolpropionic acid and dimethylolbutyric acid, the neutralizer is one or more of triethylamine and dimethylethanolamine, for a hydrophilic chain extender of methyldiethanolamine, the neutralizer is one or more of formic acid and acetic acid, and for a hydrophilic chain extender of ethylenediamine ethanesulfonic acid sodium salt and 1, 4-butanediol-2-sulfonic acid sodium salt, the neutralizer is not needed;
in the step (5), the rear chain extender is one or more of ethylenediamine, hexamethylenediamine, hydrazine hydrate and p-phenylenediamine.
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