CN107955363B - Method for modifying bio-based aqueous polyurethane emulsion by ZnO/NCC nano composite particles and product thereof - Google Patents
Method for modifying bio-based aqueous polyurethane emulsion by ZnO/NCC nano composite particles and product thereof Download PDFInfo
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- CN107955363B CN107955363B CN201711274832.2A CN201711274832A CN107955363B CN 107955363 B CN107955363 B CN 107955363B CN 201711274832 A CN201711274832 A CN 201711274832A CN 107955363 B CN107955363 B CN 107955363B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a method for modifying a bio-based aqueous polyurethane emulsion by ZnO/NCC nano composite particles, which comprises the following steps: uniformly mixing an alkali source, amines, a zinc source, nano-cellulose and water to form an alkaline solution of the nano-cellulose; carrying out hydrothermal reaction at 80-160 ℃ to obtain nano composite particles; and uniformly mixing the nano composite particles with the bio-based waterborne polyurethane. The invention also discloses modified waterborne polyurethane prepared by the method, which comprises the following components in percentage by mass: 1 part of ZnO/NCC nano composite particles and 10-100 parts of waterborne polyurethane emulsion; the ZnO/NCC nano composite particles are obtained by reacting a mixture containing the following components in percentage by mass: 5-15% of an alkali source, 6-20% of amines, 4-25% of a zinc source, 35-84.9% of water and 0.1-5% of nanocellulose. The modification method is simple, and can improve the ultraviolet resistance, the mechanical property and the like.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a method for modifying a bio-based aqueous polyurethane emulsion by ZnO/NCC nano composite particles and a product thereof.
Background
With the gradual depletion of petrochemical resources, people gradually focus on the utilization of renewable resources. The guar gum is taken from the endosperm of guar bean, contains a large amount of hydroxyl on the molecular chain, and can replace part of petrochemical resource polyol. Waterborne Polyurethane (WPU) is an environment-friendly material taking water as a dispersion medium, has the characteristics of no toxicity, difficult combustion and the like, and is widely applied to the fields of leather, coating, textile and the like. However, in the preparation process of WPU, hydrophilic groups are introduced to the molecular chain, and most of the waterborne polyurethane is in a linear structure, so that the adhesive film has low strength. WPU has relatively weak ultraviolet resistance in the application aspects of leather finishing, wall coating and the like. Therefore, the mechanical property and the ultraviolet resistance of the waterborne polyurethane emulsion are urgently needed to be improved, and if guanidine gum is introduced to the polyurethane main chain to prepare the bio-based polyurethane emulsion, the mechanical property of the waterborne polyurethane emulsion can be improved.
Nano-cellulose (NCC), a nano-grade cellulose obtained by hydrolysis of natural plant fibers. The length is 10-1000nm, the diameter is 5-20nm, and the composite material has the properties of high specific surface area, low density, high modulus, reproducibility, biodegradability and the like. The nano zinc oxide (ZnO) has the particle size of 1-100 nm and has good ultraviolet shielding performance. The research takes NCC as a template, ZnO grows to prepare ZnO/NCC nano composite particles, and the ZnO/NCC nano composite particles are physically blended and introduced into the bio-based waterborne polyurethane emulsion. Can endow the polyurethane with better ultraviolet resistance and mechanical property, and further expand the application range of the polyurethane.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for modifying a bio-based aqueous polyurethane emulsion by using ZnO/NCC nano composite particles. The obtained composite emulsion has excellent ultraviolet resistance, mechanical properties and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is that the method for modifying the bio-based aqueous polyurethane emulsion by the ZnO/NCC nano composite particles specifically comprises the following steps:
step 1: uniformly mixing an alkali source, amines, a zinc source, nano-cellulose and water to form an alkaline solution of the nano-cellulose;
step 2: and (3) putting the mixture obtained in the step (1) into a hydrothermal reaction kettle, carrying out heat preservation reaction for a period of time, and carrying out centrifugal washing to obtain ZnO/NCC composite particles.
And step 3: and (3) uniformly mixing the ZnO/NCC nano composite particles obtained in the step (2) with the bio-based aqueous polyurethane emulsion (patent number: CN 201710373705.1) to obtain the stable ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
The invention is also characterized in that:
the step 1 is specifically implemented according to the following method:
5-15% of an alkali source, 6-20% of amines, 4-25% of a zinc source, 35-84.9% of water and 0.1-5% of nano cellulose, wherein the total mass content of the components is 100%. Putting into a beaker, and stirring uniformly.
The alkali source is one or a mixture of sodium hydroxide, potassium hydroxide or barium hydroxide;
the zinc source is one of zinc chloride, zinc nitrate, zinc acetate and zinc sulfate or a mixture of the components;
the amine is one of ammonia water, hexamethylenetetramine or diethanolamine or a mixture of components thereof;
the step 2 is specifically implemented according to the following method:
and (2) putting the mixture obtained in the step (1) into a hydrothermal reaction kettle, reacting for 6-14 h at the temperature of 80-160 ℃, and centrifuging and washing to obtain the ZnO/NCC nano composite particles.
Step 3 is specifically implemented according to the following method:
step 3.1: and (2) respectively weighing the ZnO/NCC nano composite particles obtained in the step (2) and the bio-based waterborne polyurethane emulsion according to the mass ratio of 1: 10-100:
step 3.2: and (3) mixing the ZnO/NCC nano composite particles obtained in the step (3.1) with the bio-based aqueous polyurethane emulsion, and stirring for 1-6 hours to obtain the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
The invention has the beneficial effects that:
(1) the composite particles selected by the invention are a method for modifying the bio-based aqueous polyurethane emulsion by using self-made ZnO/NCC nano composite particles, and the modification method is simple;
(2) according to the method for modifying the bio-based aqueous polyurethane emulsion by using the ZnO/NCC nano composite particles, disclosed by the invention, the anti-ultraviolet property, the mechanical property and the like of the material can be further improved by adding the ZnO/NCC nano composite particles into the bio-based aqueous polyurethane.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Taking 5g of sodium hydroxide as an alkali source and 6g of industrial ammonia water as amines, weighing 5g of zinc acetate and 0.1g of nanocellulose, adding water until the total mass of the mixture is 100g, stirring for 1h until the raw materials are uniformly mixed to obtain sodium
Rice cellulose alkaline solution. And carrying out hydrothermal reaction on the nano cellulose alkaline solution at the reaction temperature of 80 ℃ for 14h, and separating, washing and drying the product to obtain the ZnO/NCC nano composite particles. According to mass
Respectively weighing ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion according to the mass ratio of 1:10, and uniformly mixing and stirring the weighed ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion for 1h to obtain the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
Example 2
Taking 5g of barium hydroxide as an alkali source, taking 6g of urea as an amine, weighing 5g of zinc acetate and 0.15g of nanocellulose, adding water until the total mass of the mixture is 100g, stirring for 2h, and uniformly mixing the raw materials to obtain the nanocellulose alkaline solution. And carrying out hydrothermal reaction on the nano cellulose alkaline solution at the reaction temperature of 100 ℃ for 12h, and separating, washing and drying the product to obtain the ZnO/NCC nano composite particles. Respectively weighing ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion according to the mass ratio of 1:20, and uniformly mixing and stirring the weighed ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion for 2 hours to obtain the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
Example 3
Taking 5g of sodium hydroxide as an alkali source, taking 6g of urea and 3g of hexamethylenetetramine as amines, weighing 8g of zinc nitrate and 0.15g of nanocellulose, adding water until the total mass of the mixture is 100g, stirring for 2h until the raw materials are uniformly mixed, and obtaining the nanocellulose alkaline solution. And carrying out hydrothermal reaction on the nano cellulose alkaline solution at the reaction temperature of 100 ℃ for 14h, and separating, washing and drying the product to obtain the ZnO/NCC nano composite particles. Respectively weighing ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion according to the mass ratio of 1:50, and uniformly mixing and stirring the weighed ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion for 2 hours to obtain the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
Example 4
Taking 10g of sodium hydroxide as an alkali source, taking 6g of urea and 7g of hexamethylenetetramine as amines, weighing 15g of zinc chloride and 2g of nanocellulose, adding water until the total mass of the mixture is 100g, and stirring for 2 hours until the raw materials are uniformly mixed to obtain the nanocellulose alkaline solution. And carrying out hydrothermal reaction on the nano cellulose alkaline solution at the reaction temperature of 120 ℃ for 10h, and separating, washing and drying the product to obtain the ZnO/NCC nano composite particles. Respectively weighing ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion according to the mass ratio of 1:60, and uniformly mixing and stirring the weighed ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion for 2h to obtain the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
Example 5
Taking 15g of sodium hydroxide as an alkali source, taking 6g of urea and 14g of diethanolamine as amines, weighing 25g of zinc sulfate and 5g of nano-cellulose, adding water until the total mass of the mixture is 100g, stirring for 2h until the raw materials are uniformly mixed, and obtaining the nano-cellulose alkaline solution. And carrying out hydrothermal reaction on the nano cellulose alkaline solution at the reaction temperature of 160 ℃ for 7h, and separating, washing and drying the product to obtain the ZnO/NCC composite particles. Respectively weighing ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion according to the mass ratio of 1:70, and uniformly mixing and stirring the weighed ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion for 2 hours to obtain the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
Example 6
The samples of examples 1 to 3 were subjected to evaluation of properties such as emulsion appearance, freeze-thaw stability, storage stability, film appearance, mechanical properties, and ultraviolet resistance under the same test conditions using an unmodified bio-based aqueous polyurethane emulsion as a blank sample, and the results in table 1 were obtained. Table 1 shows the performance test results of the modified bio-based waterborne polyurethane emulsion and the unmodified bio-based waterborne polyurethane emulsion of examples 1-3.
The data in table 1 show that the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion prepared by the invention has improved mechanical properties and ultraviolet resistance compared with blank emulsions. Wherein, the tensile strength of the sample of the example 2 is improved by 88.6 percent compared with that of a blank sample, and the elongation at break of the sample of the example 2 is reduced by 44.2 percent compared with that of the blank sample; examples 1 to 3 all exhibited a certain absorption effect against ultraviolet rays. The above results show that the invention further improves the ultraviolet resistance, mechanical properties and other properties of the material by adding ZnO/NCC nano composite particles into the waterborne polyurethane.
Claims (2)
1. A method for modifying emulsion of bio-based waterborne polyurethane by ZnO/NCC nano composite particles is characterized by comprising the following steps:
taking 5g of barium hydroxide as an alkali source, taking 6g of urea as an amine, weighing 5g of zinc acetate and 0.15g of nanocellulose, adding water until the total mass of the mixture is 100g, stirring for 2h, and uniformly mixing the raw materials to obtain a nanocellulose alkaline solution;
carrying out hydrothermal reaction on the nano cellulose alkaline solution at the reaction temperature of 100 ℃ for 12h, and separating, washing and drying the product to obtain ZnO/NCC nano composite particles;
respectively weighing ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion according to the mass ratio of 1:20, and uniformly mixing and stirring the weighed ZnO/NCC nano composite particles and the bio-based aqueous polyurethane emulsion for 2 hours to obtain the ZnO/NCC nano composite particle modified bio-based aqueous polyurethane emulsion.
2. The ZnO/NCC nanocomposite particle modified bio-based waterborne polyurethane prepared by the method of claim 1.
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| CN110919804B (en) * | 2019-11-07 | 2021-02-19 | 浙江省林业科学研究院 | Bamboo wood enhanced synergistic treatment method |
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