CN113817132A - Preparation method of environment-friendly amine-free special fluorescent polyurethane emulsion protective agent - Google Patents

Preparation method of environment-friendly amine-free special fluorescent polyurethane emulsion protective agent Download PDF

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CN113817132A
CN113817132A CN202011438542.9A CN202011438542A CN113817132A CN 113817132 A CN113817132 A CN 113817132A CN 202011438542 A CN202011438542 A CN 202011438542A CN 113817132 A CN113817132 A CN 113817132A
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environment
protective agent
polyurethane emulsion
preparation
emulsion protective
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孙鹏飞
王津阳
马艳华
张贵梓
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Hanzhong Juzhida Yuanhuanneng Technology Co ltd
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Hanzhong Juzhida Yuanhuanneng Technology Co ltd
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Abstract

The invention provides a preparation method of an environment-friendly amine-free special fluorescent polyurethane emulsion protective agent, which comprises the steps of adding polyglycol, diisocyanate and a hydrophilic chain extender into a drying reactor for polymerization reaction to obtain a polyurethane prepolymer; adding a chain extender, a fluorescent agent and an antioxidant, reacting for a period of time, and cooling; finally, adding a tannic acid aqueous solution under high-speed stirring for reaction and emulsification to obtain the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent. In the preparation process, no organic solvent is added, and natural product tannic acid is introduced; the sulfonate type hydrophilic chain extender is adopted, an amine pH regulator is not required to be added for neutralization in the synthesis process, the production process is simpler, and the sulfonate type hydrophilic chain extender has the characteristics of environmental friendliness, no toxicity, no harm, safety, biodegradability and the like, and can be widely used in special operation.

Description

Preparation method of environment-friendly amine-free special fluorescent polyurethane emulsion protective agent
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a preparation method of an environment-friendly amine-free special fluorescent polyurethane emulsion protective agent.
Background
With the improvement of the quality of life of human beings, environmental regulations are more and more strict, and various environmental regulations strictly limit the discharge amount of Volatile Organic Compounds (VOC) and the content of harmful solvents, so that the waterborne polyurethane product which is produced by more environment-friendly biomass raw materials and is not added with the harmful solvents becomes one of the main development directions of coatings, adhesives, fabric finishing, leather and synthetic leather finishing.
In special operation, the waterborne polyurethane has the advantages of low toxicity, difficult combustion, no environmental pollution, energy conservation, safety, reliability and the like, is better popularized and applied than solvent type polyurethane, and is more compliant with the requirements of national safety and environmental protection laws and regulations. However, compared with solvent-based polyurethanes, the water-based polyurethanes have the disadvantages of poor water resistance, acid and alkali resistance and mechanical properties due to the introduction of hydrophilic groups such as carboxyl, hydroxyl and the like into the molecular structure. In addition, because the conventional waterborne polyurethane adopts the carboxylic acid type hydrophilic chain extender, an amine pH regulator needs to be added for neutralization in the synthesis process, and amines are volatile and toxic and can cause damage to human bodies; one of the raw materials of the waterborne polyurethane is polyester polyol or polyether polyol, the source of the waterborne polyurethane is mainly petroleum at present, the petroleum resource is gradually exhausted, and if biomass based on natural renewable resources is adopted to replace or partially replace the polyol or the waterborne polyurethane is modified, the energy crisis caused by the petroleum resource can be relieved, the environmental pollution caused by non-degradable high polymer materials can be reduced, and the current sustainable development requirement is met. The literature reports the synthesis of waterborne polyurethanes from different bio-based raw materials, such as the synthesis of modified waterborne polyurethanes from castor oil and soybean oil. However, in the experimental processes, vegetable oil needs to be converted into available polyols, so that the cost of the product is inevitably increased, and the popularization and application of the product are limited.
Disclosure of Invention
Aiming at the defects of the prior art and overcoming the defects of poor water resistance, solvent resistance and mechanical property of the existing waterborne polyurethane, the invention provides the preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent which is low in cost, simple in process, environment-friendly and biodegradable.
The technical scheme provided by the invention is as follows: a preparation method of an environment-friendly amine-free special fluorescent polyurethane emulsion protective agent comprises the following steps:
(1) adding the polyglycol, diisocyanate and hydrophilic chain extender into a drying reactor, and carrying out polymerization reaction at 75-90 ℃ for 1-4h, wherein the mass ratio of diisocyanate to polyglycol is 0.4-0.9: 1, the mass ratio of diisocyanate to hydrophilic chain extender is 2-8: 1;
(2) adding chain extender 1, 4-butanediol, fluorescent agent and antioxidant into a reactor to react for 1-4h at 60-80 ℃, wherein the addition of the fluorescent agent accounts for 0.05-0.1% of the mass of the whole system, and the addition of the antioxidant accounts for 0.005-0.05% of the mass of the whole system;
(3) under high-speed stirring, mixing the mixture with the mass concentration of 0.3-2% and the mass ratio of diisocyanate of 0.02-0.1: 1, adding the aqueous solution of tannic acid into a reactor, and reacting for 2-5h at the temperature of 30-50 ℃ to obtain the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent;
in the step (1), the hydrophilic chain extender is a sulfonate type and is one or a mixture of more of ethylenediamine ethanesulfonic acid sodium salt, 1, 4-butanediol-2-sodium sulfonate and 1, 2-dihydroxy-3-propanesulfonic acid sodium salt in any proportion.
Further, the polyglycol in the step (1) is polyether diol or polyester diol, and the number average relative molecular mass of the polyether diol and the polyester diol is 1000 or 2000 respectively.
Further, the polyether diol is polyoxypropylene diol or polytetrahydrofuran ether diol, and the polyester diol is polycaprolactone diol, polycarbonate diol or polybutylene adipate diol.
Further, the isocyanate in the step (1) is isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or diphenylmethane diisocyanate.
Further, the mass ratio of the 1, 4-butanediol to the polyglycol in the step (2) is 0.025-0.12: 1.
further, the fluorescer in the step (2) adopts one or a mixture of several of NFW, MST-L, ER-1, DT and BACL in any proportion.
Further, the antioxidant in the step (2) is one or a mixture of several hindered phenol antioxidants 1010, 168, 204 and 1076 in any proportion.
Further, the stirring speed in the step (3) is 1000-.
The raw materials such as the antioxidant, the fluorescent agent and the like are purchased from the market.
Compared with the prior art, the invention has the advantages that:
(1) the average functionality of hydroxyl in the molecular structure of the tannic acid is 15, and the multiple functionality-OH becomes a reactive functional group of the crosslinking modified polyurethane. The multifunctional tannic acid links linear polyurethane macromolecular chains together in a chemical bond form to form polyurethane resin with a net structure, and a sulfonate hydrophilic chain extender is adopted, so that a cross-linked and modified waterborne polyurethane coating film can show good water resistance, thermal stability and mechanical property;
(2) the tannic acid is a natural product, has the advantages of natural degradability, wide source, low price and the like, can partially replace polyol to synthesize polyurethane, not only improves the comprehensive performance of the waterborne polyurethane, but also can relieve the energy crisis caused by petroleum resources, reduce the environmental pollution caused by non-degradable high polymer materials and greatly reduce the raw material cost of the product;
(3) according to the invention, the sulfonate type hydrophilic chain extender is adopted, the amine pH regulator is not required to be added in the synthesis process, and the synthesis process is simpler;
(4) the invention introduces fluorescent agent and antioxidant, increases the oxidation resistance of the product, can meet the operation requirement of special industry, and does not need to add toxic and harmful organic solvent in the whole preparation process, thereby not only eliminating the pollution and damage to the environment, operation and use personnel, but also improving the application effect of the product.
Drawings
FIG. 1 is a TG diagram of a polyurethane film;
FIG. 2 is a graph of the fluorescence analysis of a polyurethane emulsion;
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
An environment-friendly amine-free special fluorescent polyurethane emulsion protective agent is prepared by the following method:
1) firstly, adding polycaprolactone diol, isophorone diisocyanate and 1, 2-dihydroxy-3-sodium propane sulfonate into a drying reactor to carry out a polymerization isophorone reaction at 75 ℃, wherein the mass ratio of isophorone diisocyanate to polycaprolactone diol is 0.74: 1, the mass ratio of isophorone diisocyanate to 1, 2-dihydroxy-3-sodium propane sulfonate is 5.6: 1; the reaction time is 4 h;
2) adding a chain extender 1, 4-butanediol, 0.05% of fluorescer NFW and 0.005% of antioxidant 1010 into a reactor at 65 ℃ for reaction for 3 hours, wherein the mass ratio of the 1, 4-butanediol to the polycaprolactone diol is 0.051: 1;
3) under the stirring of 1000r/min, adding a 0.89% aqueous tannic acid solution into the reactor to react for 2.5 hours at 45 ℃, wherein the mass ratio of isophorone diisocyanate to tannic acid is 14.51: 1, obtaining the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent.
Example 2
An environment-friendly amine-free special fluorescent polyurethane emulsion protective agent is prepared by the following method:
1) firstly, adding polytetrahydrofuran ether dihydric alcohol, hexamethylene diisocyanate and 1, 4-butanediol-2-sodium sulfonate into a drying reactor to carry out polymerization reaction at 75 ℃, wherein the mass ratio of the hexamethylene diisocyanate to the polytetrahydrofuran ether dihydric alcohol is 0.67: the mass ratio of 1, hexamethylene diisocyanate to 1, 4-butanediol-2-sodium sulfonate is 5.27: 1; the reaction time is 3 h;
2) adding a chain extender 1, 4-butanediol, 0.06% of fluorescer MST-L and 0.01% of antioxidant 168 into a reactor at 70 ℃ for reaction for 2 hours, wherein the mass ratio of the 1, 4-butanediol to the polytetrahydrofuran ether glycol is 0.027: 1;
3) under the stirring of 1300r/min, adding a 0.6 mass percent aqueous tannic acid solution into the reactor, and reacting for 5 hours at 30 ℃, wherein the mass ratio of hexamethylene diisocyanate to tannic acid is 13.35: 1, obtaining the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent.
Example 3
An environment-friendly amine-free special fluorescent polyurethane emulsion protective agent is prepared by the following steps:
1) firstly, adding polyoxypropylene glycol, toluene diisocyanate and sodium 1, 2-dihydroxy-3-propanesulfonate into a drying reactor to perform polymerization reaction at 80 ℃, wherein the mass ratio of the toluene diisocyanate to the polyoxypropylene glycol is 0.52: the mass ratio of 1, toluene diisocyanate to 1, 2-dihydroxy-3-propanesulfonic acid sodium salt is 2.9: 1; the reaction time is 2 h;
2) adding a chain extender 1, 4-butanediol, 0.07% of fluorescer ER-1 and 0.03% of antioxidant 204 into a reactor at 60 ℃ for reaction for 4 hours, wherein the mass ratio of the 1, 4-butanediol to the polyoxypropylene glycol is 0.063: 1;
3) under the stirring of 2000r/min, adding a 0.36% tannic acid aqueous solution into the reactor to react for 3 hours at 40 ℃, wherein the mass ratio of the toluene diisocyanate to the tannic acid is 11.77: 1, obtaining the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent.
Example 4
An environment-friendly amine-free special fluorescent polyurethane emulsion protective agent is prepared by the following steps:
1) firstly, adding polycarbonate diol, diphenylmethane diisocyanate and 1, 4-butanediol-2-sodium sulfonate into a drying reactor, and carrying out polymerization reaction at 85 ℃, wherein the mass ratio of the diphenylmethane diisocyanate to the polycarbonate diol is 0.65: the mass ratio of 1, diphenylmethane diisocyanate to 1, 4-butanediol-2-sodium sulfonate is 3.26: 1; the reaction time is 1.5 h;
2) adding a chain extender 1, 4-butanediol, 0.08% of a fluorescent agent DT and 0.04% of an antioxidant 1076 into a reactor, and reacting at 75 ℃ for 1.5h, wherein the mass ratio of the 1, 4-butanediol to the polycarbonate diol is 0.0405: 1;
3) and adding 1% tannic acid aqueous solution into a reactor under the stirring of 2500r/min, and reacting for 2h at 50 ℃ to obtain the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent. Wherein the mass ratio of the diphenylmethane diisocyanate to the tannic acid is 13.98: 1;
example 5
An environment-friendly amine-free special fluorescent polyurethane emulsion protective agent is prepared by the following steps:
1) firstly, adding polybutylene adipate diol, isophorone diisocyanate and ethylene diamine sodium ethanesulfonate into a drying reactor, and carrying out polymerization reaction at 90 ℃, wherein the mass ratio of isophorone diisocyanate to polybutylene adipate diol is 0.71: 1, the mass ratio of isophorone diisocyanate to ethylenediamine ethanesulfonic acid sodium salt is 5.55: 1; the reaction time is 2.5 h;
2) adding a chain extender 1, 4-butanediol, 0.1% of a fluorescent agent BACL and 0.05% of an antioxidant 1010 into a reactor, and reacting for 1h at 80 ℃, wherein the mass ratio of the 1, 4-butanediol to the polybutylene adipate diol is 0.081: 1;
3) under the stirring of 3000r/min, adding 1.2% by mass of tannic acid aqueous solution into the reactor, and reacting for 4 hours at 35 ℃, wherein the mass ratio of isophorone diisocyanate to tannic acid is 14.36: 1, obtaining the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent.
Comparative example 1
A common polyurethane emulsion protective agent is prepared by the following steps:
1) firstly, adding polycaprolactone diol, isophorone diisocyanate and dimethylolpropionic acid into a drying reactor to carry out isophorone polymerization reaction at 75 ℃, wherein the mass ratio of isophorone diisocyanate to polycaprolactone is 0.74: 1, the mass ratio of isophorone diisocyanate to dimethylolpropionic acid is 5.67: 1; the reaction time is 4 h;
2) adding a chain extender 1, 4-butanediol into the reactor at 65 ℃ for reaction for 3 hours, wherein the mass ratio of the 1, 4-butanediol to the polycaprolactone is 0.051: 1;
3) cooling to 25 ℃, adding triethylamine to adjust the pH value of the reaction system to 7, and reacting for 2.5 h;
4) adding deionized water to emulsify for 30min under the stirring of 1000r/min to obtain the common polyurethane emulsion protective agent.
Performance testing
The following performance analysis was performed with respect to the urethane emulsion protectors obtained in examples 1 to 5 and comparative examples.
1. Thermogravimetric (TG) analysis
TG analysis was performed using a thermogravimetric analyzer model Q500 from TA of America under the following experimental operating conditions: the sample mass is about 5mg, the temperature rise rate is 20 ℃/min under the nitrogen atmosphere, and the temperature rise interval is 20-600 ℃.
Fig. 1 is a TG diagram of the polyurethane films of example 1 and comparative example 1, wherein WPU0 represents comparative example 1, WPU3 represents example 1, and table 1 is thermal weight loss ratio data of the polyurethane films before and after modification.
TABLE 1 thermal weight loss ratio data of polyurethane film before and after modification
Figure BDA0002821486970000081
Note: t is1、T2、T3、T4、T5、T6Respectively represent decomposition temperatures at 10%, 20%, 40%, 60%, 80% and 90% weight loss ratios of polyurethane.
As can be seen from FIG. 1, the waterborne polyurethane modified by tannic acid has good thermal stability. As can be seen from Table 1, the decomposition temperature of the modified aqueous polyurethane adhesive film is increased when the weight loss ratio is the same, which indicates that the thermal stability of the modified polyurethane adhesive film is improved, and the overall decomposition temperature is slightly higher than that of the unmodified polyurethane.
2. Fluorescence test
The prepared biomass fluorescence modified aqueous polyurethane emulsion was subjected to fluorescence test using a fluorescence spectrophotometer model F-4600 from Hitachi, Japan.
As shown in FIG. 2, which is a graph showing the fluorescence analysis of the polyurethane emulsions of examples 1 to 5 and comparative example 1, it can be seen from FIG. 2 that the polyurethane emulsion has the fluorescence characteristic after the addition of the fluorescent agent, and the fluorescence characteristic is stronger as the amount of the fluorescent agent added increases.
3. Mechanical Property test
The dried adhesive film was cut into a dumbbell shape, and the stretching performance was tested by an electronic universal stretcher (New Sansi materials testing Co., Ltd., Shenzhen) controlled by an SANS microcomputer at room temperature. The thicknesses of three different places of the dumbbell-shaped glue film are measured, averaged and input into a computer. Then, tensile test was carried out in accordance with GB/T528-.
4. Oxidation resistance test
And respectively measuring the glossiness of the polyurethane film after the polyurethane film is initially placed for one month, and evaluating the oxidation resistance of the polyurethane film according to the change condition of the glossiness. Gloss was measured according to CB/T1743-79(89) standard using a 60 reflection angle measuring instrument. The oxidation resistance is calculated as follows:
Figure BDA0002821486970000101
delta-film oxidation resistance,%; o-the initial gloss of the adhesive film; o0Gloss after 1 month of storage
Table 2 shows the mechanical property and oxidation resistance test data of the polyurethane emulsion protective agent adhesive films prepared in examples 1-5 and comparative example 1, and it can be seen from Table 2 that the modified polyurethane has strong rigidity, increased cohesive energy and improved adhesive film tensile strength to a certain extent after tannic acid is added, and the oxidation resistance shows an enhanced trend along with the increase of the antioxidant addition.
TABLE 2 mechanical Properties and Oxidation resistance of the adhesive films
Sample name Tensile strength/MPa Elongation at break/% Oxidation resistance%
Example 1 7.01 305.78 92.35
Example 2 6.12 318.93 94.23
Example 3 4.53 331.24 95.45
Example 4 8.09 271.23 97.34
Example 5 8.45 243.23 98.67
Comparative example 1 4.23 212.19 90.23
The comprehensive performance test results show that the fluorescent polyurethane emulsion protective agent prepared by modifying the tannic acid has strong rigidity, increased cohesive energy, improved tensile strength of a glue film to a certain extent and better thermal stability, and the sulfonic acid type hydrophilic chain extender is adopted in the invention, so that an amine pH regulator is not required to be added in the synthesis process, the synthesis process is simpler, and the antioxidant performance of the product is improved by an antioxidant, so that the prepared fluorescent polyurethane emulsion protective agent has better effect and stronger practicability compared with the existing fluorescent polyurethane emulsion protective agent.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. A preparation method of an environment-friendly amine-free special fluorescent polyurethane emulsion protective agent is characterized by comprising the following steps:
(1) adding the polyglycol, diisocyanate and hydrophilic chain extender into a drying reactor, and carrying out polymerization reaction at 75-90 ℃ for 1-4h, wherein the mass ratio of diisocyanate to polyglycol is 0.4-0.9: 1, the mass ratio of diisocyanate to hydrophilic chain extender is 2-8: 1;
(2) adding chain extender 1, 4-butanediol, fluorescent agent and antioxidant into a reactor to react for 1-4h at 60-80 ℃, wherein the addition of the fluorescent agent accounts for 0.05-0.1% of the mass of the whole system, and the addition of the antioxidant accounts for 0.005-0.05% of the mass of the whole system;
(3) under high-speed stirring, mixing the mixture with the mass concentration of 0.3-2% and the mass ratio of diisocyanate of 0.02-0.1: 1, adding the aqueous solution of tannic acid into a reactor, and reacting for 2-5h at the temperature of 30-50 ℃ to obtain the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent;
in the step (1), the hydrophilic chain extender is a sulfonate type and is one or a mixture of more of ethylenediamine ethanesulfonic acid sodium salt, 1, 4-butanediol-2-sodium sulfonate and 1, 2-dihydroxy-3-propanesulfonic acid sodium salt in any proportion.
2. The preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent as claimed in claim 1, characterized in that: the polyglycol in the step (1) is polyether diol or polyester diol, and the number average relative molecular mass of the polyether diol and the polyester diol is 1000 or 2000 respectively.
3. The preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent as claimed in claim 2, characterized in that: the polyether diol is polyoxypropylene diol or polytetrahydrofuran ether diol, and the polyester diol is polycaprolactone diol, polycarbonate diol or polybutylene adipate diol.
4. The preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent as claimed in claim 1, characterized in that: the isocyanate in the step (1) is isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate or diphenylmethane diisocyanate.
5. The preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent as claimed in claim 1, characterized in that: the mass ratio of the 1, 4-butanediol to the polyglycol in the step (2) is 0.025-0.12: 1.
6. the preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent as claimed in claim 1, characterized in that: the fluorescer in the step (2) adopts one or a mixture of more of NFW, MST-L, ER-1, DT and BACL in any proportion.
7. The preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent as claimed in claim 1, characterized in that: the antioxidant in the step (2) is one or a mixture of several hindered phenol antioxidants 1010, 168, 204 and 1076 in any proportion.
8. The preparation method of the environment-friendly amine-free special fluorescent polyurethane emulsion protective agent as claimed in claim 1, characterized in that: the stirring speed in the step (3) is 1000-3000 r/min.
CN202011438542.9A 2020-12-07 2020-12-07 Preparation method of environment-friendly amine-free special fluorescent polyurethane emulsion protective agent Pending CN113817132A (en)

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