CN109796569B - Application of vegetable oil-based water-based polyurethane emulsion as setting product and hair setting product - Google Patents
Application of vegetable oil-based water-based polyurethane emulsion as setting product and hair setting product Download PDFInfo
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Abstract
The invention discloses application of a vegetable oil-based waterborne polyurethane emulsion as a setting product and a hair setting product. The vegetable oil-based waterborne polyurethane emulsion is prepared by adopting vegetable oil-based polyalcohol and using at least one of DMPA, DMBA and MDEA as a chain extender. The emulsion has mature preparation process, simple process, easy control and convenient industrial production; and the hair styling product has excellent styling effect, and provides a new material source for the hair styling product.
Description
Technical Field
The invention belongs to the field of application of waterborne polyurethane, and particularly relates to application of a vegetable oil-based waterborne polyurethane emulsion as a setting product and a hair setting product.
Background
Hair styling spray products can hold hair in a particular shape, provide temporary styling benefits to the hair, can be rinsed off with water or shampoo, have a significant impact on various hair styles and fashion trends, and are widely used throughout the world. Conventional hair styling sprays generally rely on a multi-component formulation, such as CN1081913C to provide a hair styling composition: 0.1% to 15% by weight of a silicone grafted adhesive polymer, 0.5% to 15% by weight of a hydrocarbon solvent, 80% to 98.9% by weight of the composition of a polar solvent (water, a mixture of C2-C3 monoalcohols) and various plasticizers (acetyl tri C2-C8 alkyl citrate). The polymer in the hair styling component is also polyvinylpyrrolidone, its copolymer with vinyl acetate and maleic anhydride, alcohol and ether polymer or some natural polymer, and various additives and organic solvents. While the hair styling products have good styling effects, certain toxicity is inevitably generated to human bodies due to complex components of the hair styling products, and the polymers with complex formulas are easy to cause environmental pollution in the synthesis process. Therefore, it would be of great interest to develop a biosafety hair styling product that is simple in construction and composition.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the application of the vegetable oil-based waterborne polyurethane emulsion as a shaping product.
The invention also provides a hair styling product based on the vegetable oil-based aqueous polyurethane emulsion.
The purpose of the invention is realized by the following technical scheme:
the application of the vegetable oil-based aqueous polyurethane emulsion as a shaping product is characterized in that the vegetable oil-based aqueous polyurethane emulsion is prepared by the following steps: diisocyanate, vegetable oil-based polyol and a chain extender are mixed according to a molar ratio of (1.7-2.2): 1: (0.69-1.19), heating, adding a catalyst for catalytic reaction, cooling to room temperature after the reaction is finished, adding a neutralizing agent for neutralization, and adding water for emulsification reaction to obtain the vegetable oil-based waterborne polyurethane emulsion.
Preferably, the styling product is a hair styling product.
The vegetable oil-based waterborne polyurethane is applied to the field of hair styling, and has good biological safety.
The vegetable oil-based polyol is a whole vegetable oil-based polyol which is started from one or more than two of soybean oil, linseed oil, olive oil, rapeseed oil, castor oil and grape seed oil.
The chain extender is one or more than two of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA) and N-Methyldiethanolamine (MDEA).
The catalyst is dibutyltin dilaurate (DBTDL), the dosage of the catalyst accounts for 0.2-0.5% of the total mass of the material, and the catalytic reaction condition is that the stirring reaction is carried out for 1.5-2.5 h at the temperature of 70-85 ℃;
the neutralizing agent is one or more than two of triethylamine, N-dimethylethanolamine or glacial acetic acid, the neutralization degree is 50-97%, and the time of the neutralization reaction is 5-30 min;
the reaction conditions of the emulsification reaction are as follows: the rotating speed of the stirrer is 400-800 r/min, and the emulsifying time is 1.5-2.5 h.
The solid content of the vegetable oil-based waterborne polyurethane emulsion is 10-25%.
A hair styling product based on vegetable oil-based waterborne polyurethane emulsion is prepared from vegetable oil-based waterborne polyurethane emulsion and water, wherein the solid content of the vegetable oil-based waterborne polyurethane in the hair styling product is 1-10 wt%; the vegetable oil-based waterborne polyurethane emulsion is prepared by the following steps: diisocyanate, vegetable oil-based polyol and a chain extender are mixed according to a molar ratio of (1.7-2.2): 1: (0.69-1.19), heating, adding a catalyst for catalytic reaction, cooling to room temperature after the reaction is finished, adding a neutralizing agent for neutralization, adding water for emulsification, and evaporating to remove the solvent to obtain the vegetable oil-based waterborne polyurethane emulsion.
The hair styling product based on the vegetable oil-based aqueous polyurethane emulsion has single component, the solvent is water, and no other substances are contained.
After the hair styling product based on the vegetable oil-based water-based polyurethane emulsion is coated, the moisture absorption rate is less than or equal to 6%, the ultraviolet transmittance is more than or equal to 99%, the Young modulus is more than or equal to 50Mpa, and the breaking elongation is between 30% and 300%.
In the hair styling product, the vegetable oil-based polyol is one or more than two vegetable oil-based polyols selected from soybean oil, linseed oil, olive oil, rapeseed oil, castor oil and grape seed oil.
In the hair styling product, the chain extender is one or more than two of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA) and N-Methyldiethanolamine (MDEA).
In the hair setting product, the catalyst is dibutyltin dilaurate (DBTDL), the dosage of the catalyst accounts for 0.2-0.5% of the total mass of the material, and the catalytic reaction condition is that the mixture is stirred and reacts for 1.5-2.5 h at the temperature of 70-85 ℃;
in the hair styling product, the neutralizing agent is one or more than two of triethylamine, N-dimethylethanolamine or glacial acetic acid, the neutralization degree is 50-97%, and the neutralization reaction time is 5-30 min;
in the hair styling product, the reaction conditions of the emulsification reaction are as follows: the rotating speed of the stirrer is 400-800 r/min, and the emulsifying time is 1.5-2.5 h.
In the hair styling product, the solid content of the vegetable oil-based waterborne polyurethane emulsion is 10-25%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the hair styling product based on the vegetable oil-based aqueous polyurethane emulsion provided by the invention is single in component, excellent in styling effect and very good in biological safety.
(2) The method has the advantages of mature preparation process, simple process, easy control and convenient industrial production.
(3) The invention adopts the all-natural vegetable oil-based polyol to prepare the waterborne polyurethane, replaces the traditional polymer dihydric alcohol or polyol from petrochemical sources, opens up a new application field for natural materials, improves the use value of the waterborne polyurethane, and relieves the pressure of petrochemical industry.
Drawings
FIG. 1 shows transmittance of the vegetable oil-based aqueous polyurethane emulsion of the comparative examples and examples of the present invention in the visible light and ultraviolet light ranges.
Fig. 2 hair styling efficiency (a) of the vegetable oil-based aqueous polyurethane emulsion of the present invention and examples 1-24 and the styling pictures (B) of some examples, wherein L0 in (B) means the initial curl length of hair and L1.5 means the length of hair after hanging curls in an environment of 25 ℃ and 75 ± 5% RH for 1.5 hours.
Fig. 3 shows skin irritation of the vegetable oil-based aqueous polyurethane emulsion prepared according to the example of the present invention (blank control area, black frame test area), 20% Sodium Dodecyl Sulfate (SDS) was selected as a positive control, and commercially available gel water was used as a comparative example.
FIG. 4 is a H & E pathological diagram of skin tissues of the vegetable oil-based aqueous polyurethane emulsion prepared by the embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The preparation methods of various vegetable oil-based polyols used in the examples are described in the references Zhang, C, et al (2015), "Biobased polyurethanes prepared from differential flexible table oils," ACS applied Mater Interfaces 7(2):1226 and 1233 ], and have the general structural formula:
wherein R is1And R2Is a fatty acid.
Example 1
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and DMBA (calculated according to hydroxyl value) are mixed according to the mol ratio of 1.7: 1.0: 0.69 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt%, stirring is continued for 2h (methyl ethyl ketone (MEK) is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to the room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 400r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 2
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and DMBA (calculated according to hydroxyl value) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.2 wt% is added, stirring is continued for 2h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content.
Example 3
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short is calculated according to hydroxyl value) and DMBA (calculated according to hydroxyl value) are mixed according to the mol ratio of 2.0: 1.0: 0.99 of the emulsion is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.5 wt%, stirring is continued for 2h (if the solution viscosity is increased, acetone is added into the system until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 500r/min, deionized water is added for emulsification for 2h, and finally the emulsion is transferred to a single-mouth round-bottom flask to be subjected to rotary evaporation to remove the acetone, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid.
Example 4
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and DMBA (calculated according to hydroxyl value) are mixed according to the mol ratio of 2.2: 1.0: 1.19 placing the mixture into a double-mouth round-bottom flask, adjusting the rotating speed of a stirrer to 200r/min, mechanically stirring and mixing the mixture for 10min under the heating of an oil bath at 78 ℃, adding DBTDL accounting for 0.3 wt% of the total mass of the materials, continuing stirring for 2h (if the solution viscosity is increased, adding MEK into the system until the reaction system can flow), cooling to room temperature, adding triethylamine for neutralization for 30min (the neutralization degree is 97%), increasing the rotating speed to 450r/min, adding deionized water for emulsification for 2h, and finally transferring the emulsion into a single-mouth round-bottom flask for rotary evaporation to remove MEK, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of 12-13% can be obtained.
Example 5
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.7: 1.0: 0.69 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt%, stirring is continued for 2h (MEK is added into the system until the reaction system can flow if the solution viscosity is increased), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of 12-13.
Example 6
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 600r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content.
Example 7
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 2.0: 1.0: 0.99 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (if the solution viscosity is increased, acetone is added into the system until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 800r/min, deionized water is added for emulsification for 1.5h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the acetone is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 8
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 2.2: 1.0: 1.19 placing the mixture into a double-mouth round-bottom flask, adjusting the rotating speed of a stirrer to 200r/min, mechanically stirring and mixing the mixture for 10min under the heating of an oil bath at 78 ℃, adding DBTDL accounting for 0.4 wt% of the total mass of the materials, continuing stirring for 2h (if the solution viscosity is increased, adding MEK into the system until the reaction system can flow), then cooling to room temperature, adding triethylamine for neutralization for 30min (the neutralization degree is 97%), increasing the rotating speed to 450r/min, adding deionized water for emulsification for 2.5h, and finally transferring the emulsion into a single-mouth round-bottom flask to carry out rotary evaporation to remove MEK, thus obtaining the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of 10%.
Example 9
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl value) are mixed according to the mol ratio of 1.7: 1.0: 0.69 is placed in a double-mouth round bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of 70 ℃ oil bath, DBTDL with the total mass of materials being 0.4 wt%, stirring is continued for 2h (MEK is added into the system until the reaction system can flow if the solution viscosity is increased), then cooling is carried out to room temperature, glacial acetic acid is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 1.5h, finally the emulsion is transferred to a single-mouth round bottom flask, and the MEK is removed through rotary evaporation, so that the cationic vegetable oil-based waterborne polyurethane emulsion with the solid content of 15.
Example 10
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl value) are mixed according to the mol ratio of 0.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, after mechanical stirring and mixing are carried out for 10min under the heating of 78 ℃ oil bath, DBTDL with the total mass of materials being 0.2 wt% is added, stirring is continued for 2.0h (if the solution viscosity is increased, MEK is added into the system until the reaction system can flow), then cooling is carried out to the room temperature, glacial acetic acid is added for neutralization for 30min (the neutralization degree is 97%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the cationic vegetable oil-based waterborne polyurethane emulsion with the solid.
Example 11
IPDI (calculated according to isocyanic acid radical), castor oil base polyol (COP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl value) are mixed according to the mol ratio of 2.0: 1.0: 0.99 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.5 wt% is added, stirring is continued for 2.5h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, glacial acetic acid is added for neutralization for 10min (the neutralization degree is 97%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the.
Example 12
IPDI (calculated according to isocyanic acid radical), olive oil base polyol (OCP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl group) are mixed according to the mol ratio of 2.0: 1.0: 1.19 placing the mixture into a double-mouth round-bottom flask, adjusting the rotating speed of a stirrer to 200r/min, mechanically stirring and mixing the mixture for 10min under the heating of an oil bath at 78 ℃, adding DBTDL accounting for 0.3 wt% of the total mass of the materials, continuing stirring for 2h (if the solution viscosity is increased, adding MEK into the system until the reaction system can flow), then cooling to room temperature, adding glacial acetic acid for neutralization for 30min (the neutralization degree is 97%), increasing the rotating speed to 450r/min, adding deionized water for emulsification for 2h, and finally transferring the emulsion into a single-mouth round-bottom flask to carry out rotary evaporation to remove the MEK, thus obtaining the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of 10%.
Example 13
IPDI (calculated according to isocyanic acid radical), rapeseed oil-based polyol (CaCP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (if the solution viscosity is increased, acetone is added into the system until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 50%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the acetone is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 14
IPDI (calculated according to isocyanic acid radical), grape seed oil base polyol (GCP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 in a double-mouth round-bottom flask, adjusting the rotating speed of a stirrer to 200r/min, mechanically stirring and mixing for 10min under the heating of oil bath at 78 ℃, adding DBTDL accounting for 0.3 wt% of the total mass of materials, continuing stirring for 2h (if the solution viscosity is increased, MEK is added into the system until the reaction system can flow), then cooling to room temperature, adding triethylamine for neutralization for 30min (the neutralization degree is 60%), increasing the rotating speed to 450r/min, adding deionized water for emulsification for 2h, and finally transferring the emulsion into a single-mouth round-bottom flask for rotary evaporation to remove MEK, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of 12-13% can be obtained.
Example 15
IPDI (calculated according to isocyanic acid radical), soybean oil-based polyol (SCP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system until the reaction system can flow if the solution viscosity is increased), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 70%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 16
IPDI (calculated according to isocyanic acid radical), linseed oil polyol (LCP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 80%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 17
IPDI (calculated according to isocyanic acid radical), olive oil base polyol (OCP for short, calculated according to hydroxyl value) and DMPA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 90%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based aqueous polyurethane emulsion with the solid
Example 18
IPDI (calculated according to isocyanic acid radical), olive oil base polyol (OCP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 50%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content.
Example 19
IPDI (calculated according to isocyanic acid radical), rapeseed oil-based polyol (CaCP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (if the solution viscosity is increased, acetone is added into the system until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 60%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the acetone is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 20
IPDI (calculated according to isocyanic acid radical), grape seed oil base polyol (GCP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 70%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, and finally the emulsion is transferred to a single-mouth round-bottom flask to be subjected to rotary evaporation to remove MEK, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the.
Example 21
IPDI (calculated according to isocyanic acid radical), soybean oil-based polyol (SCP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl value) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system if the solution viscosity is increased until the reaction system can flow), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 80%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 22
IPDI (calculated according to isocyanic acid radical), linseed oil polyol (LCP for short, calculated according to hydroxyl value) and MDEA (calculated according to hydroxyl group) are mixed according to the mol ratio of 1.85: 1.0: 0.84 is placed in a double-mouth round-bottom flask, the rotating speed of a stirrer is adjusted to be 200r/min, mechanical stirring and mixing are carried out for 10min under the heating of oil bath at 78 ℃, DBTDL with the total mass of materials being 0.3 wt% is added, stirring is continued for 2h (MEK is added into the system until the reaction system can flow if the solution viscosity is increased), then cooling is carried out to room temperature, triethylamine is added for neutralization for 30min (the neutralization degree is 90%), the rotating speed is increased to 450r/min, deionized water is added for emulsification for 2h, finally the emulsion is transferred to a single-mouth round-bottom flask, and the MEK is removed through rotary evaporation, so that the anionic vegetable oil-based waterborne polyurethane emulsion with the solid content of.
Example 23
The emulsion obtained in example 1 was diluted to 1% solids.
Example 24
The emulsion obtained in example 1 was diluted to 10% solids.
Comparative example
Sanxuan shaping gel stock solution
In order to investigate the relationship between the physical and chemical properties and the hair styling effect of the prepared vegetable oil-based waterborne polyurethane, the waterborne polyurethane emulsion obtained in each of the examples 1-24 is poured into a mold, then placed into a 30 ℃ oven for 12-48 h, then placed into a 60 ℃ oven for 12-72 h, and finally placed into a 60 ℃ vacuum oven for 12-72 h, so as to obtain the waterborne polyurethane film.
The following tests were carried out on the aqueous polyurethane emulsion or polyurethane film obtained in each example, and the results are shown in tables 1 and 2
The invention has been tested as follows:
1. particle size and stability testing: the particle size was characterized by a Zeta-sizer Zeta-sizer Nano ZSE, the results of which are shown in Table 1. The particle size of the emulsion obtained in the examples 1-22 is between 30 and 200 nm; stability testing the emulsions were centrifuged at 3000rpm for 30min with no precipitation or delamination indicating that they were stable for 1 year at room temperature (Lin X, Zhang S, Qian J. Synthesis and properties of a novel UV-curable waterborne polyurethane. journal of Coatings Technology and research. 2014; 11:319-28.) this experiment centrifuged the vegetable oil-based aqueous polyurethane emulsions of examples 1-24 for 1h, both to find precipitation and delamination indicating that they were stable for more than two years at room temperature. The results are shown in Table 1.
2. And (3) testing tensile property: the aqueous polyurethane films obtained in the examples were cut into specimens having a length of 25mm and a width of 10mm, and mechanical properties of the films were measured at a tensile rate of 100mm/min using a universal mechanical tester (model Shimadzu AGS-X), and Young's modulus of the samples was determined from a stress-strain curve, and the results are shown in Table 2.
3. Contact angle test: a contact angle test was performed by dropping 3. mu.l of deionized water on the surface of the polyurethane films obtained in examples 1 to 22. The test instrument is Drop Shape Analysis System DSA 100 (Kruss, Hamburg, Germany), and the results are shown in Table 2, and the obtained polyurethane films all have certain hydrophilicity.
4. Transmittance: after releasing the examples 1, 4, 8, 14, 18 to 3% solids, 200. mu.l of each film was formed (1 cm. times.1 cm area) and the transmittance of the film was measured by UV-2550, and the comparative example measured the transmittance directly from 200. mu.l of the film. The obtained transmittance results are shown in fig. 1, and in the examples and comparative examples, the transmittance was 99% or more in the visible light range, and the transmittance of the examples of the present invention was higher.
5. And (3) moisture absorption rate test: in the literature (Kang SY, Ji Z, Tseng LF, Turner SA, Villanueva DA, Johnson R, et al design and Synthesis of Waterborn polyurethanes. advanced materials.2018; 30: e1706237), the method was tested by adding 4mL of the vegetable oil-based aqueous polyurethane emulsion obtained in examples 1-22 to a weighed dish (Wp), drying in an oven at 60 ℃ for 3 days, and then equilibrating in an environment at 40 ℃ and 45. + -. 2% Relative Humidity (RH) for 16h and weighing (W0). The films were then placed at 40 ℃ in an environment of 80. + -. 2% Relative Humidity (RH) for 18h and the weighed (Wt) moisture pick-up was calculated according to the following formula, and the results are shown in Table 2:
6. hair styling effect test: the aqueous polyurethane emulsions obtained in examples 1 to 24 were each diluted to 3% solids by the methods described in the reference (Kang SY, Ji Z, Tseng LF, Turner SA, Villanueva DA, Johnson R, et al design and Synthesis of Waterborn polyurethanes advanced materials.2018; 30: e1706237), and together with examples 25, 26, 1ml of each dilution was coated on 2.0g of hair and combed 10 times thoroughly, and blown dry with a blower. The hair was curled up using a curling iron (diameter 35mm, temperature 120 ℃) and set for 10seconds, the initial curl length (L0) for 10seconds was recorded at this point, then the curls were suspended in an environment of 25 ℃ and 75. + -. 5% RH for 90 minutes, the length of hair at this point (Lf) was recorded, and the setting ratio (Rs) of the sample to the hair was calculated according to the following formula, and the results are shown in FIG. 2:
Rs(％)＝Lf/L0×100％
7. comprehensively analyzing the moisture absorption rate, the tensile property and the hair setting effect of the plant oil-based waterborne polyurethane film obtained in the embodiment to obtain: when the moisture absorption rate of the polyurethane film is less than or equal to 6 percent, the Young modulus is more than or equal to 50MPa, and the elongation at break is 30-300 percent, the examples have good hair styling effect.
8. Skin irritation test: skin irritation experiments were performed according to international standards (ISO 10993-10).
Experimental animals: new zealand white rabbits (3 per experimental group); the state is as follows: adult, healthy, non-invasive, unproductive and infertile. 24h before the test, the hairs on the two sides of the spine of the experimental animal are cut off, the epidermis cannot be damaged, and the hair removing range is 3cm x 3cm respectively on the left side and the right side.
The test method comprises the following steps: the vegetable oil-based aqueous polyurethane emulsion of example 1, example 4, example 8, example 14, example 18 was diluted to 3% solids and approximately 0.5ml of the test substance was applied directly to the dehaired skin and then covered with two layers of gauze (2.5cm x 2.5cm) and a layer of cellophane paper and secured with a non-irritating adhesive plaster and bandage. The other side of the skin is used as a blank control (0.5ml of normal saline), and the positive substance is 20% SDS according to the standard requirement; the commercial control was comparative example 1, using a blocking test, with an application time of 4 h. The skin reaction at the site of application was observed at 1, 24, 48 and 72h after sample removal. Thereafter, New Zealand white rabbits were treated with CO2Death by peace and happinessTaking skin tissue in the test range, fixing in 4% paraformaldehyde solution, and placing in a container&E, dyeing and observing: the fixed tissue is sequentially dehydrated by ethanol gradient, xylene is transparent, and the fixed tissue is soaked in paraffin for 30min and 3 times each time. Embedding, making into wax block, cutting into slices with thickness of about 5 μm, dewaxing with xylene, hydrating with gradient ethanol, washing with water, and staining with hematoxylin for 5-20 min. Then washing with tap water for 3-5min, differentiating with 1% hydrochloric acid ethanol for 5-30s, washing with tap water for 1-3min to obtain weakly alkaline aqueous solution for 30s-1min, washing with tap water for 5-10min, adding into eosin dye solution (dyeing cytoplasm) for 5-15min, dehydrating with gradient ethanol, sealing with xylene, and observing under microscope.
And (3) testing results: the skin reaction results of the smeared parts at 1 hour, 24 hours, 48 hours and 72 hours after the sample is removed are shown in a figure 3, the positive control shows obvious erythema and redness, a small erythema appears after 1 hour of removing the dressing from the sand Xuan gel in the market, but the erythema disappears after 1 day, which shows that the irritation of the sand Xuan gel to the skin is negligible, and the erythema and redness are not found at the observation time point in all the embodiments of the invention, which shows that the obtained vegetable oil-based waterborne polyurethane has no irritation to the skin; the H & E staining result is shown in figure 4, the epithelial tissue of the positive control sample is widely eroded, the blood vessel congestion is accompanied with severe blood vessel rupture, and the positive control sample has a large amount of inflammatory cell (leukocyte) infiltration, the epithelial tissue of all the tested examples, comparative examples and blank controls is normal, intact, free from the blood vessel congestion phenomenon, and the leukocyte infiltration phenomenon is very few, which indicates that the plant oil-based waterborne polyurethane prepared by the invention has no skin irritation.
TABLE 1 particle size, pH and storage stability of inventive examples 1-22
TABLE 2 contact angle, moisture absorption rate, Young's modulus, tensile strength and elongation at break for inventive examples 1-22
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A hair styling product based on vegetable oil-based waterborne polyurethane emulsion is characterized in that the hair styling product is prepared from vegetable oil-based waterborne polyurethane emulsion and water, and the solid content of the vegetable oil-based waterborne polyurethane in the hair styling product is 1-10 wt%; the vegetable oil-based waterborne polyurethane emulsion is prepared by the following steps: diisocyanate, vegetable oil-based polyol and a chain extender are mixed according to a molar ratio of (1.7-2.2): 1: (0.69-1.19), uniformly mixing, heating, adding a catalyst for catalytic reaction, cooling to room temperature after the reaction is finished, adding a neutralizing agent for neutralization, adding water for emulsification, and evaporating to remove the solvent to obtain the vegetable oil-based waterborne polyurethane emulsion;
the vegetable oil-based polyol is vegetable oil-based polyol which is started from one or more than two of soybean oil, linseed oil, olive oil, rapeseed oil, castor oil and grape seed oil;
after the hair styling product based on the vegetable oil-based water-based polyurethane emulsion is coated, the moisture absorption rate is less than or equal to 6%, the ultraviolet transmittance is more than or equal to 99%, the Young modulus is more than or equal to 50Mpa, and the breaking elongation is between 30% and 300%.
2. The hair styling product based on the vegetable oil-based aqueous polyurethane emulsion as claimed in claim 1, wherein the chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid and N-methyldiethanolamine.
3. The hair styling product based on the vegetable oil-based aqueous polyurethane emulsion is characterized in that the catalyst is dibutyltin dilaurate, the amount of the catalyst is 0.2-0.5% of the total mass of the material, and the catalytic reaction is carried out under the condition of stirring at the temperature of 70-85 ℃ for 1.5-2.5 h;
the neutralizing agent is one or more than two of triethylamine, N-dimethylethanolamine or glacial acetic acid, the neutralization degree is 50-97%, and the time of the neutralization reaction is 5-30 min;
the reaction conditions of the emulsification reaction are as follows: the rotating speed of the stirrer is 400-800 r/min, and the emulsifying time is 1.5-2.5 h.
4. The hair styling product based on the vegetable oil-based aqueous polyurethane emulsion as claimed in claim 1, wherein the vegetable oil-based aqueous polyurethane emulsion has a solid content of 10-25%.
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| CN107157807A (en) * | 2017-06-08 | 2017-09-15 | 广州天赐高新材料股份有限公司 | A kind of Hairsetting compositions and preparation method thereof |
| CN108467467A (en) * | 2018-05-02 | 2018-08-31 | 江苏维特金属防腐科技有限公司 | Plant oil base Anionic Water-borne Polyurethane Emulsion and its preparation method and application |
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| US5883175A (en) * | 1994-09-05 | 1999-03-16 | Daikin Industries Ltd. | Stainproofing composition having water-and-oil-repellency |
| CN101904805A (en) * | 2008-06-13 | 2010-12-08 | 香港理工大学 | Give the nursing agent and the method for hair style memory effect |
| CN107157807A (en) * | 2017-06-08 | 2017-09-15 | 广州天赐高新材料股份有限公司 | A kind of Hairsetting compositions and preparation method thereof |
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