阅读说明：本技术 一种生物基水性聚氨酯树脂及其应用 (Bio-based waterborne polyurethane resin and application thereof ) 是由 李维虎 王启东 朱保凌 黄星 郭文鹤 戴家兵 于 2019-10-18 设计创作，主要内容包括：本发明公开了一种生物基水性聚氨酯树脂及其应用,其中,生物基水性聚氨酯树脂至少包括75-95质量份的生物基大分子多元醇,10-20质量份的生物基异氰酸酯,0.05-0.5质量份的碳量子点组分。本发明能提高生物基水性聚氨酯树脂的剥离强度、耐磨性等性能。(The invention discloses a bio-based waterborne polyurethane resin and application thereof, wherein the bio-based waterborne polyurethane resin at least comprises 75-95 parts by mass of bio-based macromolecular polyol, 10-20 parts by mass of bio-based isocyanate and 0.05-0.5 part by mass of carbon quantum dot component. The invention can improve the performances of the bio-based waterborne polyurethane resin such as peel strength, wear resistance and the like.)

1. The bio-based waterborne polyurethane resin is characterized by at least comprising the following components in parts by mass:

the carbon quantum dots are particles with hydroxyl structures and are used for chemically modifying the bio-based waterborne polyurethane resin.

2. The bio-based aqueous polyurethane resin according to claim 1, wherein the quantum yield of the carbon quantum dots is 5% to 7%.

3. The bio-based aqueous polyurethane resin according to claim 1, wherein the preparation method of the carbon quantum dots comprises the following steps:

mixing the juice with a solvent and heating to obtain a dark brown material;

filtering the dark brown substance to obtain a filtrate;

and adding the solvent into the filtrate and carrying out surface treatment to obtain the carbon quantum dots.

4. The bio-based aqueous polyurethane resin according to claim 3, wherein the fruit juice is a pulp-free banana juice.

5. The bio-based aqueous polyurethane resin according to claim 3, wherein the solvent comprises any one or more of ethanol, acetone, methanol and propanol.

6. The bio-based aqueous polyurethane resin according to claim 1, wherein the bio-based macromolecular polyol comprises any one or more combination of castor oil, soybean oil, palm oil polyol, rosin ester polyol and castor oil derivative polyol.

7. The bio-based aqueous polyurethane resin according to claim 1, wherein the bio-based isocyanate comprises any one or more of dimer acid diisocyanate, bio-based 1, 4-butylene diisocyanate, and bio-based 1, 5-pentylene diisocyanate.

8. The bio-based aqueous polyurethane resin according to claim 1, wherein the small molecule polyol chain extender comprises any one or more combination of trimethylolpropane, glycerol, butanediol, ethylene glycol, 1, 3-propanediol polyether polyol and cyclohexanedimethanol.

9. The bio-based aqueous polyurethane resin according to claim 1, wherein the carboxylic acid type hydrophilic chain extender comprises any one or a combination of two of dimethylolpropionic acid and dihydroxybutyric acid.

10. Use of a bio-based aqueous polyurethane resin according to any one of claims 1 to 9 in clothing leather.

Technical Field

The invention belongs to the technical field of polyurethane resin synthesis, and particularly relates to a bio-based waterborne polyurethane resin and application thereof.

Background

The bio-based macromolecular polyol and the bio-based isocyanate are prepared from vegetable oil, so that the raw material resources are rich, the price is low, and the acquisition ways are more; the bio-based waterborne polyurethane resin has the advantages of better degradability, environmental friendliness and the like, and accords with the current concept of green environmental protection; the development of bio-based waterborne polyurethane resin can reduce or even eliminate the use of petroleum polyols, and the use of vegetable oil polyols can not only save energy and excessively utilize, but also promote the development of agriculture, so the development of bio-based waterborne polyurethane resin has very important significance. However, the existing bio-based waterborne polyurethane resin has the defects of insufficient folding resistance, wear resistance, heat resistance, mechanical property, storage property, biodegradability, constant temperature and humidity property and the like. The carbon quantum has the advantages of high length-diameter ratio, good mechanical property, good heat resistance and the like, so that various properties of the bio-based waterborne polyurethane can be improved by introducing the carbon quantum dots into the bio-based waterborne polyurethane.

Disclosure of Invention

In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a bio-based aqueous polyurethane resin and applications thereof, which can significantly improve the folding resistance, wear resistance, heat resistance, mechanical properties, storage properties, biodegradability, constant temperature and humidity properties, and the like of the aqueous polyurethane resin.

To achieve the above and other objects, the present invention is accomplished by the following technical solutions,

the invention provides a bio-based waterborne polyurethane resin, which at least comprises the following components in parts by mass:

the carbon quantum dots are particles with hydroxyl structures and are used for chemically modifying the bio-based waterborne polyurethane resin.

In one embodiment, the quantum yield of the carbon quantum dots is 5% -7%. The preparation method of the carbon quantum dot comprises the following steps:

mixing the juice with a solvent and heating to obtain a dark brown material;

filtering the dark brown substance to obtain a filtrate;

and adding the solvent into the filtrate and carrying out surface treatment to obtain the carbon quantum dots.

In one embodiment, the juice is a pulp-free banana juice.

In one embodiment, the solvent comprises any one or combination of ethanol, acetone, methanol, and propanol.

In one embodiment, the bio-based macro-polyol comprises any one or combination of castor oil, soybean oil, palm oil polyol, rosin ester polyol, and castor oil derivative polyol.

In one embodiment, the bio-based isocyanate comprises any one or more of dimer acid diisocyanate, bio-based 1, 4-butylene diisocyanate and bio-based 1, 5-pentylene diisocyanate.

In one embodiment, the small molecule polyol chain extender comprises any one or more combination of trimethylolpropane, glycerol, butanediol, ethylene glycol, 1, 3-propanediol polyether polyol, and cyclohexanedimethanol.

In one embodiment, the carboxylic acid type hydrophilic chain extender includes any one or a combination of two of dimethylolpropionic acid and dihydroxybutyric acid.

In one embodiment, the small molecule amine post-chain extender comprises any one or more of ethylenediamine, hexamethylenediamine, isophoronediamine.

In one embodiment, the neutralizing agent comprises any one or more of triethylamine, diethanolamine, and triethanolamine

The invention also aims to provide application of the bio-based waterborne polyurethane resin in clothing leather.

The carbon quantum dots used in the invention have a large number of hydroxyl structures, and are easy to carry out in-situ polymerization with waterborne polyurethane. The bio-based waterborne polyurethane resin is mainly prepared from bio-based isocyanate and bio-based macromolecular polyol, and the effective combination of the nano-structure carbon quantum dots and the bio-based waterborne polyurethane is realized through an in-situ polymerization technology, so that various performances of the bio-based waterborne polyurethane can be improved through the special structure of the carbon quantum dots. Tests show that the carbon quantum dots can greatly improve the folding resistance, the wear resistance, the heat resistance, the mechanical property, the storage property, the biodegradability and the constant temperature and humidity performance of the bio-based waterborne polyurethane fabric resin. According to the invention, no organic solvent is required to be added in the process of preparing the bio-based aqueous polyurethane dispersion, so that the environmental pollution is avoided, and the aims of low carbon, environmental protection and energy conservation are achieved.

Drawings

Fig. 1 is a schematic flow chart of a preparation method of the carbon quantum dot of the present invention.

Detailed Description

The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.

When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.

Note that "%" and "part(s)" shown in the description herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.

The invention provides a bio-based waterborne polyurethane resin and application thereof, wherein carbon quantum dots are introduced into the bio-based waterborne polyurethane resin for modification, so that higher folding resistance, wear resistance, heat resistance, mechanical property, storage property, biodegradability and constant temperature and humidity property are obtained, and the modified bio-based waterborne polyurethane resin is applied to clothing leather.

Referring to fig. 1, the method for preparing the carbon quantum dots according to the present invention includes:

s1, mixing the fruit juice with the solvent and heating to obtain a dark brown substance;

s2, filtering the dark brown substance to obtain a filtrate;

s3, adding the solvent into the filtrate, and carrying out surface treatment to obtain the carbon quantum dots.

Specifically, in step S1, the heating is performed under the condition of heating at 160 ℃ for 4 to 5 hours. The fruit juice is banana juice without pulp. The solvent comprises any one or more of ethanol, acetone, methanol and propanol. The solvent has a cleaning effect.

Specifically, in step S3, the surface treatment step includes separating larger particles from the filtrate by using a centrifuge, taking the remaining filtrate, and finally drying the remaining filtrate under reduced pressure to obtain the carbon quantum dots, where the carbon quantum dots are semisolid carbon quantum dots.

In various embodiments, the quantum yield of the carbon quantum dots includes 5-5.2%, 5.5-6%, 6.4-6.5%, and 6.8% -7%. The invention uses the carbon quantum dots with the carbon quantum yield within the range of 5-7 percent, can well modify the bio-based waterborne polyurethane resin, for example, the carbon quantum dots have different influences under different process conditions, the higher the hydroxyl content and the quantum yield are, the better the hydroxyl content and the quantum yield are, the lower the hydroxyl content and the quantum yield are, the worse the hydroxyl content and the quantum yield are, and the modified bio-based waterborne polyurethane resin has better comprehensive performance within the range of various raw materials of the invention. The mass of the carbon quantum dots comprises 0.05-1g, 0.05-1g, 0.05-1g and 0.1-0.2 g. The dosage of the bio-based macromolecular polyol comprises 75-80g, 86-88g and 89-95 g. The dosage of the bio-based isocyanate comprises 15-18g, 18-20g and 10-14 g. The proportion of the bio-based macromolecular polyol and the bio-based isocyanate has certain influence on the performance of the prepared bio-based waterborne polyurethane, such as peeling strength, wear resistance and the like. The dosage of the micromolecule amine post-chain extender such as ethylenediamine and the neutralizing agent such as trimethylolpropane is 4-5g, and the dosage of the micromolecule amine post-chain extender is the same as that of the neutralizing agent, so that the chain extension is more sufficient, and the modification of the carbon quantum dots is more facilitated.

The following lists some preparation processes of bio-based waterborne polyurethane resin modified by introducing carbon quantum dots and compares the performances of the modified resins.

Referring to Table 1, properties of the A resin prepared in one example are shown in Table 1. The preparation process of the resin A specifically comprises the following steps: in one embodiment, 75-80g of castor oil derivative polyol (relative molecular weight is 1000) is weighed and placed into a reactor, 18-20g of dimer acid diisocyanate is added under stirring, the temperature is kept at 80-90 ℃, and stirring is carried out for 2-3 hours. And then adding 2-2.5g of dimethylolpropionic acid (DMPA), controlling the temperature to be 80-90 ℃, stirring for 2-3 hours, continuously adding 4-5g of a small molecular polyol chain extender, keeping the temperature to be 80-90 ℃, stirring for 2-3 hours, finally adding 0.05-0.1g of carbon quantum dots, and continuously reacting for 1-2 hours at 80-90 ℃ to obtain the carbon quantum dot modified bio-based waterborne polyurethane prepolymer. And (2) cooling the aqueous polyurethane prepolymer to 5-8 ℃, adding 1.5-2g of triethylamine, stirring for 10-15 minutes, transferring to a high-speed emulsifying machine, adding 200-220 g of deionized water at the rotation speed of 1400-1600 rpm, and adding 4-5g of ethylenediamine after 1-3 minutes to obtain the carbon quantum dot modified resin A. In the embodiment, the quantum yield of the carbon quantum dots is 5-5.2%, the surface of the carbon quantum dots contains a large number of hydroxyl structures, the bio-based aqueous polyurethane resin is modified, the folding resistance, the wear resistance, the solvent resistance, the mechanical property, the storage property and the constant temperature and humidity property of the bio-based aqueous polyurethane resin are greatly improved, the peel strength of the fabric can reach 90-100KN/m, the wear resistance reaches 18-20 ten thousand times, and the heat resistance can reach 180 ℃ when the bio-based aqueous polyurethane resin is applied to the fabric.

Referring to Table 1, the properties of the B resin prepared in one example are shown in Table 1. The preparation process of the resin B specifically comprises the following steps: in one embodiment, 86-88g of castor oil derivative polyol (relative molecular weight is 1000) is weighed and placed into a reactor, 15-18g of dimer acid diisocyanate is added under stirring, the temperature is kept at 80-90 ℃, and the stirring is carried out for 2-3 hours. And then adding 2-2.5g of dimethylolpropionic acid (DMPA), controlling the temperature to be 80-90 ℃, stirring for 2-3 hours, continuously adding 4-5g of a small molecular polyol chain extender, keeping the temperature to be 80-90 ℃, stirring for 2-3 hours, finally adding 0.05-0.1g of carbon quantum dots, and continuously reacting for 1-2 hours at 80-90 ℃ to obtain the carbon quantum dot modified bio-based waterborne polyurethane prepolymer. And (2) cooling the aqueous polyurethane prepolymer to 5-8 ℃, adding 1.5-2g of triethylamine, stirring for 10-15 minutes, transferring to a high-speed emulsifying machine, adding 200-220 g of deionized water at the rotation speed of 1400-1600 rpm, and adding 4-5g of ethylenediamine after 1-3 minutes to obtain the carbon quantum dot modified resin B. In the embodiment, the quantum yield of the carbon quantum dots is 5.5-6%, the surface of the carbon quantum dots contains a large number of hydroxyl structures, the bio-based waterborne polyurethane resin is modified, the folding resistance, the wear resistance, the solvent resistance, the mechanical property, the storage property and the constant temperature and humidity property of the bio-based waterborne polyurethane are greatly improved, the peel strength of the fabric can reach 105-110KN/m, the wear resistance can reach 18-19 ten thousand times, and the heat resistance can reach 210 ℃ when the bio-based waterborne polyurethane resin is applied to the fabric.

Referring to Table 1, properties of the C resin prepared in one example can be obtained in Table 1. The preparation process of the resin C specifically comprises the following steps: in one embodiment, 89-95g of castor oil derivative polyol (relative molecular weight is 1000) is weighed and placed into a reactor, 18-20g of dimer acid diisocyanate is added under stirring, the temperature is kept at 80-90 ℃, and stirring is carried out for 2-3 hours. And then adding 2-2.5g of dimethylolpropionic acid (DMPA), controlling the temperature to be 80-90 ℃, stirring for 2-3 hours, continuously adding 4-5g of a small molecular polyol chain extender, keeping the temperature to be 80-90 ℃, stirring for 2-3 hours, finally adding 0.05-0.1g of carbon quantum dots, and continuously reacting for 1-2 hours at 80-90 ℃ to obtain the carbon quantum dot modified bio-based waterborne polyurethane prepolymer. And (2) cooling the aqueous polyurethane prepolymer to 5-8 ℃, adding 1.5-2g of triethylamine, stirring for 10-15 minutes, transferring to a high-speed emulsifying machine, adding 200-220 g of deionized water at the rotation speed of 1400-1600 rpm, and adding 4-5g of ethylenediamine after 1-3 minutes to obtain the carbon quantum dot modified resin C. In the embodiment, the quantum yield of the carbon quantum dots is 6.4-6.5%, the surface of the carbon quantum dots contains a large number of hydroxyl structures, the bio-based waterborne polyurethane resin is modified, the folding resistance, the wear resistance, the solvent resistance, the mechanical property, the storage property and the constant temperature and humidity property of the bio-based waterborne polyurethane are greatly improved, the peel strength of the fabric can reach 112-116KN/m, the wear resistance can reach 25-27 ten thousand times, and the heat resistance can reach 250 ℃ when the bio-based waterborne polyurethane resin is applied to the fabric.

Referring to Table 1, the properties of the D resin prepared in one example are shown in Table 1. The preparation process of the resin D specifically comprises the following steps: in one embodiment, 75-80g of palm oil polyol (relative molecular weight is 1000) is weighed and placed into a reactor, 10-14g of dimer acid diisocyanate is added under stirring, the temperature is kept at 80-90 ℃, and stirring is carried out for 2-3 hours. And then adding 2-2.5g of dimethylolpropionic acid (DMPA), controlling the temperature to be 80-90 ℃, stirring for 2-3 hours, continuously adding 4-5g of a small molecular polyol chain extender, keeping the temperature to be 80-90 ℃, stirring for 2-3 hours, finally adding 0.1-0.2g of carbon quantum dots, and continuously reacting for 1-2 hours at 80-90 ℃ to obtain the carbon quantum dot modified bio-based waterborne polyurethane prepolymer. And (2) cooling the aqueous polyurethane prepolymer to 5-8 ℃, adding 1.5-2g of triethylamine, stirring for 10-15 minutes, transferring to a high-speed emulsifying machine, adding 200-220 g of deionized water at the rotation speed of 1400-1600 rpm, and adding 4-5g of ethylenediamine after 1-3 minutes to obtain the carbon quantum dot modified D resin. In the embodiment, the quantum yield of the carbon quantum dots is 6.8-7%, the surface of the carbon quantum dots contains a large number of hydroxyl structures, the bio-based waterborne polyurethane resin is modified, the folding resistance, the wear resistance, the solvent resistance, the mechanical property, the storage property and the constant temperature and humidity property of the bio-based waterborne polyurethane are greatly improved, the peel strength of the fabric can reach 110-114KN/m, the wear resistance can reach 23-24 ten thousand times, and the heat resistance can reach 300 ℃ when the bio-based waterborne polyurethane resin is applied to the fabric.

Referring to Table 1, the properties of the comparative E-resins can be found in Table 1. The preparation process of the E resin specifically comprises the following steps: in one embodiment, 75-80g of castor oil derivative polyol (relative molecular weight is 1000) is weighed and placed into a reactor, 18-20g of dimer acid diisocyanate is added under stirring, the temperature is kept at 80-90 ℃, and stirring is carried out for 2-3 hours. Then 2-2.5g dimethylolpropionic acid (DMPA) is added, the temperature is still controlled at 80-90 ℃, the mixture is stirred for 2-3 hours, 4-5g of micromolecular polyol chain extender is continuously added, the temperature is kept at 80-90 ℃, and the mixture is stirred for 2-3 hours. And (2) cooling the aqueous polyurethane prepolymer to 5-8 ℃, adding 1.5-2g of triethylamine, stirring for 10-15 minutes, transferring to a high-speed emulsifying machine, adding 200-220 g of deionized water at the rotation speed of 1400-1600 rpm, and adding 4-5g of ethylenediamine after 1-3 minutes to obtain the modified E resin. In the embodiment, no carbon quantum dots are added, and the folding resistance, the wear resistance, the solvent resistance, the mechanical property, the storage property and the constant temperature and humidity property of the bio-based waterborne polyurethane prepared by the embodiment are high in performance without adding graphene oxide. The bio-based waterborne polyurethane resin is applied to the fabric, the peel strength of the fabric can reach 30-40KN/m, the wear resistance can reach 10 ten thousand times, and the heat resistance is 150 ℃.

Description of the application of the invention: the clothing leather is prepared by coating the bio-based waterborne polyurethane resin prepared by the invention on release paper as a fabric layer, then sequentially coating a middle material layer and a bottom material layer on the release paper, wherein the middle material layer and the bottom material layer are made of the bio-based waterborne polyurethane resin and other types of resins, and drying.

Performance detection

The performance test of the bio-based waterborne polyurethane fabric resin prepared in some embodiments of the invention is as follows:

(1) folding endurance: the results of the room temperature folding endurance test are shown in table 1.

(2) Wear resistance: the martindale abrasion tester shows the abrasion test results as shown in table 1.

(3) Solvent resistance: i.e., DOP resistance, and DOP solvent soak test, the test results are shown in table 1.

(4) Mechanical properties: the tensile tester tests and the tensile strength test results are shown in table 1.

(5) Storage performance: the test was carried out in an oven at 50 ℃ and the test results are shown in Table 1.

(6) And (3) constant temperature and humidity test: the results of the constant temperature and humidity test by the constant temperature and humidity tester are shown in table 1.

TABLE 1 Performance test Table

As shown in Table 1, compared with the bio-based waterborne polyurethane resin prepared without adding the carbon quantum dots, the folding resistance, the wear resistance, the heat resistance, the mechanical property, the storage property, the biodegradability and the constant temperature and humidity performance of the bio-based waterborne polyurethane resin prepared by adding the carbon quantum dots are greatly improved.

The invention introduces carbon quantum dots in the synthetic process of the bio-based waterborne polyurethane resin, thereby improving the performance of the bio-based waterborne polyurethane resin. The bio-based waterborne polyurethane resin is mainly prepared from bio-based isocyanate and bio-based macromolecular polyol according to a certain proportion at a proper reaction temperature, the carbon quantum dots are prepared by using pulp-free banana juice, and then the carbon quantum dot modified bio-based waterborne polyurethane fabric resin is prepared by using an in-situ polymerization technology. In-situ polymerization is to fill the reaction monomer between layers of the nano-layered material and to cause the reaction monomer to generate polymerization reaction between the layers. The bio-based waterborne polyurethane resin modified by the carbon quantum dots has a good degradation effect and is beneficial to environmental protection.

Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention which may be practiced, nor is it intended to limit the relative changes or modifications to the scope of the invention which may be practiced without materially changing the technical details.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.