Preparation method of bio-based self-crosslinking pigment
By polymerizing natural vinyl porphyrin and ethylene polymerizable monomers, bio-based self-crosslinked pigments are prepared, which solves the problem of poor color fastness of existing natural pigments and realizes self-crosslinking and high bonding reduces environmental pollution and difficulty in use.
Patent Information
- Application Number
- CN202411426530.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-14
- Publication Date
- 2025-01-10
AI Technical Summary
The color fastness of existing natural pigments is poor, and a large amount of color fixing agent and adhesive are required to add, resulting in environmental pollution and inconvenience in use.
The free radical polymerization of natural vinyl porphyrin colored substances and ethylene polymerizable monomers is used to prepare bio-based self-crosslinked pigments, which can be spontaneously fixed after printing and dyeing, avoiding the addition of additional color fixing agents, and improving color fastness and adhesion. .
It has achieved bio-based self-crosslinked pigments with low biological toxicity and good stability, with good color fastness and chemical resistance, reducing environmental pollution and difficulty in use.
Smart Images
Figure CN119285833A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method for preparing a bio-based self-crosslinking pigment, and belongs to the fields of textile dyeing and finishing, fine chemicals and engineering manufacturing. Background Art
[0002] At present, the harm to the environment caused by the production and use of pigments is mainly reflected in resource consumption, waste generation, and possible emission of toxic and hazardous substances. In the production process of traditional pigments, non-renewable mineral resources are often used as raw materials, and the mining of these resources often causes damage to the ecological environment and resource depletion. In the process of pigment production, wastewater, waste gas and solid waste are also generated. If not properly handled, these wastes will pollute the soil, water sources and air, posing a serious threat to the ecosystem and human health. In addition, some pigments themselves or their metabolites are toxic. If they are not strictly managed and controlled during use, they may accumulate and amplify through the food chain, causing long-term negative impacts on the environment and biodiversity. Traditional bio-based, because the pigment has no interaction with the target substrate, it is necessary to add substances such as cross-linking agents during use, which further increases the environmental burden of pigment use.
[0003] In response to these problems, some researchers have simply extracted colored substances from animals and plants to prepare natural pigments, thereby reducing harm to the environment. However, traditional natural pigments have poor color fastness due to the lack of interaction with the substrate, so they have not been used on a large scale. In order to further increase color fastness and dyeing rate, a large amount of adhesives, color fixing agents, etc. need to be added during the printing and dyeing process, which inadvertently increases the difficulty of wastewater treatment after the use of the pigment. Summary of the invention
[0004] Technical issues:
[0005] In view of the problems that existing natural pigments have poor color fastness and need to add additional additives such as fixing agents during use, a bio-based self-cross-linking pigment with low biotoxicity, good stability, natural degradation and good environment is provided. The color-forming component of the pigment is a natural bio-based colorant, which can be spontaneously fixed after printing and dyeing. No additional fixing agent needs to be added during use. After printing and dyeing, it can have good color fastness without washing. While improving color fastness, it ensures excellent adhesion and chemical resistance, thereby enhancing the applicability and reliability of the pigment.
[0006] Technical conception:
[0007] The natural vinyl porphyrin colored substance selected by the present invention has the characteristics of bright color and easy polymerization under alkaline conditions, and is commonly found in various green plant leaves, microbial body fluids and animal blood in nature. Based on free radical polymerization, natural vinyl porphyrin is polymerized with ethylene polymerizable monomers to prepare thermoplastic color latex particle pigments, which can be dried and stored after acid washing. After being configured as a printing and dyeing liquid, the target substrate is colored, and after baking, the cross-linking and color fixing can be achieved. The bio-based self-cross-linking pigment has good color fastness and avoids the drawbacks of poor color fastness of bio-based dyes on the market and the need to add additional color fixing agents during printing and dyeing.
[0008] Technical solution:
[0009] To achieve the above object, the technical solution of the present invention is as follows:
[0010] The invention provides a method for preparing a bio-based self-crosslinking pigment, which uses bio-based materials as colorants to prepare a self-crosslinking polymer pigment.
[0011] Preferably, the preparation method comprises the following steps:
[0012] 1) mixing 10-80 parts of polymerizable monomers, 30-100 parts of water, 1-5 parts of alkali agent, 3-50 parts of bio-based colorant, and 0-2 parts of buffer, and introducing inert gas into the system for protection;
[0013] 2) Raise the temperature while stirring, add a proper amount of polymerization initiator when the temperature reaches 55-95°C, keep warm and continue stirring for 4-24 hours to carry out polymerization reaction;
[0014] 3) After the reaction solution is cooled to room temperature, it is filtered using filter paper, acid-washed and neutralized, separated and dried to obtain a bio-based self-crosslinking pigment.
[0015] The polymer pigment is a substance obtained by copolymerizing a bio-based colorant with a polymerizable monomer, coating the bio-based colorant with the monomer, and coating the bio-based colorant after copolymerization.
[0016] The bio-based material is a vinyl-containing porphyrin ring substance, and specifically, natural vinyl-containing porphyrin ring substances such as hemin chloride and chlorophyll can be selected.
[0017] Preferably, the natural vinyl-containing porphyrin ring substances do not contain the three functional groups of azo bond, nitro group and amino group.
[0018] The polymerizable monomers are styrene, acrylic acid, methyl methacrylate, butyl methacrylate and derivatives thereof.
[0019] The carbon chain length of the polymerizable monomer is no more than 10 carbon atoms.
[0020] The glass transition temperature of the polymerized material is between 45 and 100 degrees Celsius.
[0021] The bio-based colorant accounts for no less than 1% and no more than 70% of the total mass of the polymerizable monomer and the bio-based colorant; more preferably, the proportion is no less than 10% and no more than 50%.
[0022] The alkali agent is sodium bicarbonate, sodium carbonate, weak alkaline sodium silicate, and sodium acetate.
[0023] The polymerization initiator is sodium persulfate, potassium persulfate, azoisobutyl cyanide. The mass ratio of the polymerization initiator to the total mass of the polymerizable monomer and the bio-based colorant is 1: (8-130).
[0024] The polymerization environment is a weakly alkaline environment, and the pH value of the system is 7.1-9.6.
[0025] After the polymerization is completed, the polymer needs to be acid-washed and stored in the dark under neutral or weakly acidic conditions.
[0026] The pH range of the acid used for pickling and neutralization is 6.0-6.5, and the amount used is 0.5-2.0 times the mass of the filter residue.
[0027] The present invention provides a bio-based self-crosslinking pigment based on the above method.
[0028] The present invention also provides the application of the bio-based self-crosslinking pigment in the fields of textile dyeing and finishing, fine chemicals, engineering manufacturing, etc.
[0029] Compared with the prior art, the present invention has the following advantages:
[0030] Using vinyl porphyrin-based bio-based substances as colorants, the production process is generally more environmentally friendly and sustainable than traditional petroleum-based pigments. The raw materials come from plants, microorganisms or other renewable resources, rather than relying on limited petroleum resources, which helps reduce the impact on the environment and reduces dependence on fossil fuels. At the same time, the pigment has self-crosslinking properties and can be directly dispersed and used without the addition of additional adhesives, reducing the use of additives while still having good fastness. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 The following are print color photos of Examples 1-5 and Comparative Examples 1-11. DETAILED DESCRIPTION
[0032] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are 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 making creative work are within the scope of protection of the present invention.
[0033] Material Source Disclosure:
[0034] The hemin involved in the following is from Sinopharm Chemical Reagent Co., Ltd., and the green leaves are from fresh camphor trees, willow trees, pine trees and green algae. Crude chlorophyll is extracted from the above green leaves using acetone. [For specific methods, see: Li Xuran. Study on the factors affecting the results of chlorophyll a determination in water by acetone extraction spectrophotometry [C] / / Chinese Society for Environmental Sciences. Proceedings of the 2015 Annual Conference of the Chinese Society for Environmental Sciences (Volume 1). Tianjin Environmental Monitoring Center, 2015: 8.]
[0035] Embodiment 1:
[0036] According to the weight ratio, 5 parts of sodium bicarbonate and 2 parts of PBS buffer were weighed in a three-necked flask, 100 parts of water were added to fully dissolve them, and nitrogen was introduced into the flask for 10 minutes before adding a mixture of 25 parts of styrene, 54 parts of acrylic acid and 50 parts of hemin chloride. Then, the stirring speed and nitrogen atmosphere were maintained at 310r / min, and after the temperature was raised to 70°C, 1 part of sodium persulfate was dissolved in 5 parts of deionized water, and added to the above reaction system as a polymerization initiator, and stirred at 70°C for 8 hours to fully react. After the reaction was completed, stirring was continued and the reaction was naturally cooled to room temperature, and the dispersion obtained by the reaction was filtered using a medium-speed qualitative filter paper. The filter residue was poured into an acid agent with a pH of 6.5 twice the mass of the filter residue, mixed and stirred, and then filtered to obtain the filter residue, and the bio-based self-cross-linking pigment was obtained after drying at room temperature.
[0037] A proper amount of water and 1.5% carboxymethyl cellulose thickener accounting for the total mass of the color paste were added to the self-crosslinking pigment to prepare a printing color paste with a concentration of 10wt%, which was printed on a 50 / 50 polyester-cotton blended fabric using a screen printing method. After baking and crosslinking for 3 minutes at a temperature 50 degrees Celsius higher than the Tg of the pigment, the printed fabric was taken out.
[0038] Embodiment 2:
[0039] According to the weight percentage, weigh 1 part of sodium carbonate in a three-necked flask, add 30 parts of water to fully dissolve it, and then add a mixture of 1 part of methyl methacrylate, 4 parts of acrylic acid and 3 parts of crude chlorophyll of camphor after nitrogen is passed into the flask for 10 minutes. Then, maintain a stirring speed of 280r / min and a nitrogen atmosphere, heat to 75°C, dissolve 1 part of sodium persulfate in 2 parts of deionized water, add the above reaction system as a polymerization initiator, and stir at 55°C for 12 hours to fully react. After the reaction is completed, continue to stir and cool naturally to room temperature, and filter the resulting dispersion using medium-speed qualitative filter paper. Pour the filter residue into an acid agent with a pH of 6.0 that is 0.5 times the mass of the filter residue and mix and stir, then filter to obtain the filter residue, and dry at room temperature to obtain a bio-based self-cross-linking pigment.
[0040] A proper amount of water and 1.0% of the total mass of the color paste as a gum arabic thickener were added to the self-crosslinking pigment to prepare a printing color paste with a concentration of 2wt%, which was printed on a 50 / 50 polyester-cotton blended fabric using a screen printing method. After baking and crosslinking for 3 minutes at a temperature 50 degrees Celsius higher than the Tg of the pigment, the printed fabric was taken out.
[0041] Embodiment 3:
[0042] According to the weight ratio, 3 parts of weak alkaline sodium silicate and 1 part of buffer were weighed in a three-necked flask, 80 parts of water were added to fully dissolve it, and nitrogen was introduced into the flask for 10 minutes before adding a mixture of 12 parts of butyl methacrylate, 6 parts of styrene sulfonate and 18 parts of crude chlorophyll from willow leaves. Then, the stirring speed and nitrogen atmosphere were maintained at 260r / min, and after the temperature was raised to 80°C, 1 part of azoisobutyl cyanide was dissolved in 4 parts of deionized water, and added to the above reaction system as a polymerization initiator, and stirred at 95°C for 4 hours to fully react. After the reaction was completed, stirring was continued and the reaction was naturally cooled to room temperature, and the dispersion obtained by the reaction was filtered using medium-speed qualitative filter paper. The filter residue was poured into an acid agent with a pH of 6.3 that was 1 times the mass of the filter residue, mixed and stirred, and then filtered to obtain the filter residue, and the bio-based self-cross-linking pigment was obtained after drying at room temperature.
[0043] A proper amount of water and a gelatin thickener accounting for 2.0% of the total mass of the color paste were added to the self-crosslinking pigment to prepare a printing color paste with a concentration of 20wt%, which was printed on a 50 / 50 polyester-cotton blended fabric using a screen printing method. After baking and crosslinking for 3 minutes at a temperature 50 degrees Celsius higher than the Tg of the pigment, the printed fabric was taken out.
[0044] Embodiment 4:
[0045] According to the weight, 4 parts of sodium acetate and 1.7 parts of buffer were weighed in a three-necked flask, and 94 parts of water were added to fully dissolve them. After nitrogen was introduced into the flask for 10 minutes, a mixture of 35 parts of styrene, 35 parts of acrylic acid and 3 parts of crude chlorophyll from pine needles was added. Then, the stirring speed and nitrogen atmosphere were maintained at 290r / min, and after the temperature was raised to 60°C, 1 part of potassium persulfate was dissolved in 5 parts of deionized water, and added to the above reaction system as a polymerization initiator, and stirred at 60°C for 24 hours to fully react. After the reaction was completed, stirring was continued and the reaction was naturally cooled to room temperature, and the dispersion obtained by the reaction was filtered using medium-speed qualitative filter paper. The filter residue was poured into an acid agent with a pH of 6.2 that was 1.9 times the mass of the filter residue, mixed and stirred, and then filtered to obtain the filter residue, and the bio-based self-cross-linking pigment was obtained after drying at room temperature.
[0046] A proper amount of water and 1.2% of the total mass of the color paste as a guar gum thickener were added to the self-crosslinking pigment to prepare a printing color paste with a concentration of 50wt%, which was printed on a 50 / 50 polyester-cotton blended fabric using a screen printing method. After baking and crosslinking for 3 minutes at a temperature 50 degrees Celsius higher than the Tg of the pigment, the printed fabric was taken out.
[0047] Embodiment 5:
[0048] According to the weight percentage, 2 parts of sodium carbonate were weighed in a three-necked flask, 50 parts of water were added to fully dissolve it, and nitrogen was introduced into the flask for 10 minutes before adding a mixture of 3 parts of butyl acrylate, 9 parts of acrylic acid and 10 parts of crude chlorophyll of green algae. Then, the stirring speed and nitrogen atmosphere were maintained at 260r / min, and after the temperature was raised to 80°C, 1 part of potassium persulfate was dissolved in 4 parts of deionized water, and added to the above reaction system as a polymerization initiator, and stirred at 80°C for 12 hours to fully react. After the reaction was completed, stirring was continued and the reaction was naturally cooled to room temperature, and the dispersion obtained by the reaction was filtered using a medium-speed qualitative filter paper. The filter residue was poured into an acid agent with a pH of 6.1 that was 1.7 times the mass of the filter residue, mixed and stirred, and then filtered to obtain the filter residue, and dried at room temperature to obtain a bio-based self-cross-linking pigment.
[0049] A proper amount of water and a thickener accounting for 2.2% of the total mass of the color paste were added to the self-crosslinking pigment to prepare a printing color paste with a concentration of 40wt%, which was printed on a 50 / 50 polyester-cotton blended fabric using a screen printing method. After baking and crosslinking at a temperature 50 degrees Celsius higher than the Tg of the pigment for 3 minutes, the printed fabric was taken out.
[0050] Comparative Example 1:
[0051] The difference between Comparative Example 1 and Example 1 is that 55 parts of hemin are added.
[0052] Comparative Example 2:
[0053] The difference between Comparative Example 1 and Example 2 is that 7 parts of sodium carbonate are added to make the pH value of the reaction system 9.8.
[0054] Comparative Example 3:
[0055] The difference between Comparative Example 1 and Example 2 is that 2 parts of acrylic acid are added.
[0056] Comparative Example 4:
[0057] The difference between Comparative Example 1 and Example 3 is that no pickling and neutralization is performed.
[0058] Comparative Example 5:
[0059] The difference between Comparative Example 1 and Example 3 is that an acid agent with a pH of 6.3 in an amount 3 times the mass of the filter residue is added for acid washing and neutralization.
[0060] Comparative Example 6:
[0061] The difference between Comparative Example 1 and Example 1 is that the acrylic acid is completely replaced with styrene, so that the Tg of the obtained pigment is 109 degrees Celsius.
[0062] Comparative Example 7:
[0063] The difference between Comparative Example 1 and Example 4 is that the polymerizable monomers are all replaced with isooctyl acrylate (C 11 H 20 O2). Comparative Example 8:
[0064] The difference between Comparative Example 1 and Example 1 is that no sodium bicarbonate is added, so that the pH value of the reaction system is 6.9.
[0065] Comparative Example 9:
[0066] The difference between Comparative Example 1 and Example 1 is that a nitro group is introduced into the hemin.
[0067] Comparative Example 10:
[0068] The difference between Comparative Example 1 and Example 1 is that an azo bond is introduced into the hemin.
[0069] Comparative Example 11:
[0070] The difference between Comparative Example 1 and Example 2 is that amino groups are introduced into the crude chlorophyll.
[0071] Specific test method:
[0072] Printing color (K / S value): Macbeth Colour-eye 7000A computer colorimeter is used to test its K / S value. CIE D65 standard light source, 10° observer, including ultraviolet rays, including specular components, large aperture.
[0073] Rubbing fastness: GB / T 3920-2008 "Textiles - Tests for colour fastness - Colour fastness to rubbing"
[0074] Reaction rate: The final pigment mass, as a percentage of the polymer monomers and bio-based colorants added during preparation.
[0075] The test results of Examples 1-5 and Comparative Examples 1-11 are shown in Table 2.
[0076] Table 2 Results of pigment reaction rate, printing K / S value and fastness
[0077]
[0078] The embodiments provided above are not intended to limit the scope of the present invention, and the steps described are not intended to limit the execution order thereof. Those skilled in the art may make obvious improvements to the present invention in combination with existing common knowledge, which also fall within the scope of protection defined by the claims of the present invention.
Claims
1. A method for preparing a bio-based self-crosslinking pigment, characterized in that: The pigment is a polymer with a bio-based material as a colorant, comprising the following steps: 1) mixing 10-80 parts of polymerizable monomers, 30-100 parts of water, 1-5 parts of alkali agent, 3-50 parts of bio-based colorant, and 0-2 parts of buffer, and introducing inert gas into the system for protection; 2) Raise the temperature while stirring, add a proper amount of polymerization initiator when the temperature reaches 55-95°C, keep warm and continue stirring for 4-24 hours to carry out polymerization reaction; 3) After the reaction solution is cooled to room temperature, it is filtered using filter paper, acid-washed and neutralized, separated and dried to obtain a bio-based self-crosslinking pigment.
2. The method according to claim 1, characterized in that Bio-based materials are natural vinyl-containing porphyrin ring substances.
3. The method according to claim 1, characterized in that Natural vinyl-containing porphyrin ring substances do not contain the three functional groups of azo bond, nitro group and amino group.
4. The method according to claim 1, characterized in that: The bio-based material is hemin and / or chlorophyll.
5. The method according to claim 1, characterized in that The polymer monomer is selected from any one or more of the following: styrene, acrylic acid, methyl methacrylate, butyl methacrylate and derivatives thereof.
6. The method according to claim 1, characterized in that The carbon chain length of the polymerizable monomer is no greater than 10 carbon atoms.
7. The method according to claim 1, characterized in that The glass transition temperature of the polymerized material is between 45-110 degrees Celsius.
8. The method according to any one of claims 1 to 7, characterized in that: The colorant accounts for no less than 1% and no more than 70% of the total mass of the polymerizable monomer and the bio-based colorant.
9. A bio-based self-crosslinking pigment prepared by the method according to any one of claims 1 to 8.
10. Use of the bio-based self-crosslinking pigment according to claim 9 in the fields of textile dyeing and finishing, fine chemicals, and engineering manufacturing.