Crosslinked anthraquinone-benzoquinone polymer containing arylamine bonds for cosmetic dyeing as well as preparation method and application of crosslinked anthraquinone-benzoquinone polymer
By using cross-linked anthraquinone-benzoquinone polymers containing aromatic amine bonds in cosmetic dyes, the problems of insufficient stability and color fastness of existing dyes are solved, and higher color fastness and lower color fastness are achieved. Solubility improves dyeing stability and environmental sustainability.
Patent Information
- Application Number
- CN202411549222.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-01
- Publication Date
- 2025-02-14
AI Technical Summary
Existing organic cosmetic dyes have shortcomings in stability, color fastness and water solubility, resulting in easy fading during use and possible environmental pollution.
A cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds was used to react components A, B and C during heating to prepare dyes with excellent photostability and chemical stability.
It improves the color fastness and mechanical strength of the dye, reduces solubility and pigment migration, and enhances dye stability and environmental sustainability.
Smart Images
Figure CN119431776A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of cosmetics, and more particularly to a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing, and a preparation method and application thereof. Background Art
[0002] Against the backdrop of increasingly prominent environmental issues, the cosmetics industry has an increasing demand for recyclable, environmentally friendly organic cosmetic colorants. Such organic cosmetic colorants not only have the advantages of flexible molecular design and low cost, but also provide rich colors and visual effects. However, many organic cosmetic colorants face the problems of poor stability and insufficient color fastness, resulting in easy fading during product use. In addition, their solubility in the aqueous phase may lead to pollution during production and use, seriously affecting environmental sustainability.
[0003] Therefore, how to develop a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing and its preparation method and application is a problem that technical personnel in this field urgently need to solve. Summary of the invention
[0004] In view of this, the present invention provides a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing, and a preparation method and application thereof.
[0005] In order to achieve the above object, the present invention adopts the following technical solution:
[0006] A cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics, the general structural formula of which is shown in Formula 1, Formula 2 or Formula 3:
[0007] The general structural formula is shown in Formula 1, Formula 2 or Formula 3:
[0008]
[0009] Wherein, n represents the number of repetitions of the polymer main chain unit, and its value is a natural number greater than 1.
[0010] The present invention also provides a method for preparing the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics, comprising the following steps:
[0011] (1) Adding component A and component B to component C, heating and stirring to obtain a mixed solution;
[0012] The mass ratio of component A to component C is (0.1 g to 5 g): (1 mL to 15 mL);
[0013] The mass ratio of component B to component C is (0.1 g to 5 g): (1 mL to 15 mL);
[0014] The above-mentioned component A is 1,4-benzoquinone;
[0015] The above-mentioned component B is one or more combinations of 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone or 1,2-diaminoanthraquinone;
[0016] The above component C is N,N-dimethylacetamide;
[0017] (2) The obtained mixed solution is centrifuged, and the supernatant is taken out. The supernatant is first frozen in a refrigerator, and then vacuum freeze-dried to obtain the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing.
[0018] Furthermore, in step (1), the heating temperature is 25°C to 200°C, the stirring speed is 1800 r / min, and the stirring time is 0h to 24h.
[0019] Furthermore, in step (2), the centrifugal speed is 10000 r / min and the centrifugal time is 30 min.
[0020] Furthermore, in step (2), the freezing temperature of the refrigerator is -10°C to -85°C, and the freezing time is 0h to 12h.
[0021] Furthermore, in step (2), the freezing temperature of the vacuum drying oven is -10°C to -99°C, the freezing time is 0h to 12h, and the vacuum degree is -30Bar.
[0022] The present invention also provides the use of the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing or the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing prepared by the above method in the field of cosmetic dyeing.
[0023] Beneficial effects of the present invention: The present invention prepares a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds through the reaction of components A\B\C during heating, and uses the obtained polymer in cosmetic dyes, which can solve the problems of poor dyeing stability, poor water solubility and hydrophilicity leading to uneven dyeing process and insufficient color fastness in current organic cosmetic dyes. The chemical reaction conditions involved in the present invention are mild, the method is simple and no side reactions occur. The obtained polymer can be used in the field of cosmetic technology and has broad application prospects.
[0024] It should be noted that the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds prepared by the method of the present invention has the following characteristics:
[0025] (1) The anthraquinone and benzoquinone structures have a strong conjugated system, which makes the dyes exhibit excellent light stability and chemical stability under ultraviolet and oxidative conditions, thereby improving color fastness; (2) The cross-linked structure enhances the mechanical strength and heat resistance of the polymer, reduces the solubility of the dye during use, and reduces pigment migration and fading; (3) The presence of aromatic amine bonds makes the chemical properties of the polymer more diverse, and different colors and properties can be designed by adjusting the structure of the polymer to meet market demand; (4) Many aromatic amine derivatives perform well in terms of biocompatibility, help reduce skin irritation, and are suitable for cosmetics for sensitive skin. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is a schematic diagram of the dyeing effect of the polymer in Example 1 of the present invention on the cream;
[0027] Figure 2 This is a schematic diagram of the dyeing effect of the polymer on the essence in Example 1 of the present invention;
[0028] Figure 3 This is a schematic diagram of the effect of the polymer in Example 1 of the present invention on lipstick staining;
[0029] Figure 4 Schematic diagram of dyeing stability of polymer (a) of Example 1 of the present invention and polymer (b) of Comparative Example 1;
[0030] Figure 5 This is the infrared spectrum of the polymer in Example 1 of the present invention
[0031] Figure 6 is an infrared spectrum of the polymer of Example 2 (a) and a schematic diagram of the dyeing effect on the cream (b);
[0032] Figure 7 is an infrared spectrum of the polymer of Example 3 (a) and a schematic diagram of the dyeing effect on the cream (b);
[0033] Figure 8 is an infrared spectrum of the polymer of Example 4 (a) and a schematic diagram of the dyeing effect on the cream (b);
[0034] Fig. 9 The infrared spectrum of the polymer of Example 5 (a) and the schematic diagram of the coloring effect on the cream (b) are shown. DETAILED DESCRIPTION
[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0036] Example 1
[0037] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0038] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 2,6-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 110° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0039] (2) The obtained mixed solution was centrifuged at a centrifugal speed of 10000 r / min for 30 min, and the supernatant was taken. The supernatant was first frozen in a refrigerator at a freezing temperature of -85°C for 12 h, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -99°C, and a freezing time of 12 h to obtain 5.689 g of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing. The color of the obtained polymer was bright and dark red. The synthesis route is as follows:
[0040]
[0041] Example 2
[0042] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0043] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 1,4-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 110° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0044] (2) The obtained mixed solution is centrifuged at a centrifugal speed of 10000 r / min for 30 min, and the supernatant is taken. The supernatant is first frozen in a refrigerator at a freezing temperature of -85°C for 12 h, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -99°C, and a freezing time of 12 h to obtain a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing. The general structural formula is shown in Formula 1. The obtained polymer has a dark color and a yield of 4.779 g.
[0045] The difference between this embodiment and embodiment 1 is that component B in step (1) is 1,4-diaminoanthraquinone. The other steps and parameters are the same as those in embodiment 1, and the synthesis route is as follows:
[0046]
[0047] Example 3
[0048] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0049] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 1,2-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 110° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0050] (2) The obtained mixed solution was centrifuged at a centrifugal speed of 10000 r / min for 30 min, and the supernatant was taken. The supernatant was first placed in a refrigerator for freezing at a freezing temperature of -85°C for 12 h, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -99°C, and a freezing time of 12 h to obtain a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing. The general structural formula is shown in Formula 3. The color of the obtained polymer is significantly improved and insoluble particles appear. The yield is 4.996 g. The synthesis route is shown as follows:
[0051]
[0052] The difference between this embodiment and embodiment 1 is that in step (1), B is 1,2-diaminoanthraquinone. The other steps and parameters are the same as those in embodiment 1.
[0053] Example 4
[0054] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0055] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 2,6-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 60° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0056] (2) The obtained mixed solution was centrifuged at a speed of 10000 r / min for 30 min, and the supernatant was taken. The supernatant was first frozen in a refrigerator at a freezing temperature of -85°C for 12 h, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -99°C, and a freezing time of 12 h to obtain a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing. The color of the obtained polymer transitioned from light brown to dark brown and insoluble particles still existed. Compared with Example 1, the yield did not change significantly.
[0057] The difference between this embodiment and embodiment 1 is that the heating temperature in step (1) is 60° C. The other steps and parameters are the same as those in embodiment 1.
[0058] Example 5
[0059] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0060] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 2,6-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 110° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0061] (2) The obtained mixed solution was centrifuged at a speed of 10000 r / min for 30 min, and the supernatant was taken. The supernatant was first frozen in a refrigerator at a freezing temperature of -55°C for 12 h, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -99°C, and a freezing time of 12 h to obtain a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing. The color of the obtained polymer transitioned from dark brown to dark red and insoluble particles still existed. The yield did not change significantly compared with Example 1.
[0062] The difference between this embodiment and embodiment 1 is that the freezing temperature of the refrigerator in step (2) is -55° C. The other steps and parameters are the same as those in embodiment 1.
[0063] Example 6
[0064] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0065] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 2,6-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 110° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0066] (2) The obtained mixed solution was centrifuged at a speed of 10000 r / min and a centrifugal time of 30 r / min, and the supernatant was taken. The supernatant was first frozen in a refrigerator at a freezing temperature of -85°C for 8 hours, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -99°C, and a freezing time of 12 hours to obtain a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing. The color was bright and dark red, but the yield was reduced to 5.218 g.
[0067] The difference between this embodiment and embodiment 1 is that the freezing time in the refrigerator in step (2) is 8 hours. The other steps and parameters are the same as those in embodiment 1.
[0068] Example 7
[0069] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0070] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 2,6-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 110° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0071] (2) The obtained mixed solution was centrifuged at a speed of 10000 r / min for 30 min, and the supernatant was taken. The supernatant was first frozen in a refrigerator at a freezing temperature of -85°C for 12 h, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -60°C, and a freezing time of 12 h to obtain a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing. The color was bright and dark red, but the yield was reduced to 5.118 g.
[0072] The difference between this embodiment and embodiment 1 is that the vacuum freeze drying freezing temperature in step (2) is -60° C. The other steps and parameters are the same as those in embodiment 1.
[0073] Example 8
[0074] The preparation method of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics comprises the following steps:
[0075] (1) Add 0.3 g of 1,4-benzoquinone and 0.2 g of 2,6-diaminoanthraquinone to 15 mL of N,N-dimethylacetamide, heat and stir at 110° C. for 24 h at a stirring speed of 1800 r / min to obtain a mixed solution;
[0076] (2) The obtained mixed solution was centrifuged at a speed of 10000 r / min for 30 min, and the supernatant was taken. The supernatant was first frozen in a refrigerator at a freezing temperature of -85°C for 12 h, and then vacuum freeze-dried at a vacuum degree of -30 Bar, a freezing temperature of -99°C, and a freezing time of 8 h to obtain 4.913 g of a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing.
[0077] The difference between this embodiment and embodiment 1 is that the vacuum freeze drying freezing time in step (2) is 8 hours. The other steps and parameters are the same as those in embodiment 1.
[0078] Effect test
[0079] Figure 1 This is a schematic diagram of the dyeing effect of the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing obtained in Example 1 of the present invention on the cream;
[0080] like Figure 1As shown, the prepared polymer was added to the cream. After a short stirring, the cream was fully dyed, indicating that the polymer had good water solubility.
[0081] Figure 2 This is a schematic diagram of the dyeing effect of the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing obtained in Example 1 of the present invention on the essence;
[0082] like Figure 2 As shown, the prepared polymer is added to the essence. After a short stirring, the essence is evenly dyed, indicating that the polymer has good hydrophilicity.
[0083] Figure 3 This is a schematic diagram of the effect of the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing obtained in Example 1 of the present invention on lipstick dyeing;
[0084] like Figure 3 As shown, the prepared polymer is added into lipstick. After mixing, the lipstick is evenly dyed, indicating that the polymer has good dispersibility.
[0085] Figure 4 This is a schematic diagram showing the dyeing stability comparison between the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing obtained in Example 1 of the present invention and cochineal red pigment in Comparative Example 1;
[0086] like Figure 4 As shown, the polymer of Example 1 and the lipstick dyed with Comparative Example 1 were put into deionized water. After immersion for 48 hours, the solution did not change in color, while the solution of Comparative Example 1 changed in color, indicating that the polymer of Example 1 has excellent color stability and high color fastness.
[0087] Figure 5 is the infrared spectrum of the polymer prepared in Example 1;
[0088] Figure 6 is an infrared spectrum of the polymer prepared in Example 2 and a schematic diagram of the coloring effect of the cream;
[0089] Figure 7 is an infrared spectrum of the polymer prepared in Example 3 and a schematic diagram of the coloring effect of the cream;
[0090] Figure 8 is an infrared spectrum of the polymer prepared in Example 4 and a schematic diagram of the coloring effect of the cream;
[0091] Fig. 9 It is an infrared spectrum of the polymer prepared in Example 5 and a schematic diagram of the dyeing effect on the cream.
[0092] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing, characterized in that: The general structural formula is shown in Formula 1, Formula 2 or Formula 3: Wherein, n represents the number of repetitions of the polymer main chain unit, and its value is a natural number greater than 1.
2. A method for preparing the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing according to claim 1, characterized in that: The steps include: (1) Adding component A and component B to component C, heating and stirring to obtain a mixed solution; The mass ratio of component A to component C is (0.1 g to 5 g): (1 mL to 15 mL); The mass ratio of component B to component C is (0.1 g to 5 g): (1 mL to 15 mL); The component A is 1,4-benzoquinone; The component B is one or more combinations of 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone or 1,2-diaminoanthraquinone; The component C is N,N-dimethylacetamide; (2) Centrifuging the obtained mixed solution, taking the supernatant, freezing the supernatant in a refrigerator, and then freeze-drying the supernatant in a vacuum to obtain the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing.
3. The method for preparing a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing according to claim 2, characterized in that: In step (1), the heating temperature is 25°C to 200°C, the stirring speed is 1800 r / min, and the stirring time is 0h to 24h.
4. The method for preparing a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics according to claim 2, characterized in that: In step (2), the centrifugal speed is 10000r / min and the centrifugal time is 30min.
5. The method for preparing a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics according to claim 2, characterized in that: In step (2), the freezing temperature of the refrigerator is -10°C to -85°C, and the freezing time is 0h to 12h.
6. The method for preparing a cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for dyeing cosmetics according to claim 2, characterized in that: In step (2), the freezing temperature of the vacuum drying oven is -10°C to -99°C, the freezing time is 0h to 12h, and the vacuum degree is -30Bar.
7. Use of the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing according to claim 1 or the cross-linked anthraquinone-benzoquinone polymer containing aromatic amine bonds for cosmetic dyeing prepared by the method according to any one of claims 2 to 6 in the field of cosmetic dyeing.