CN107445905B - Pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent and preparation method and application thereof - Google Patents
Pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, which is characterized in that the structural formula of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent is shown as a formula 1:the invention aims to provide a pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, a preparation method and application thereof. The pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent has higher whiteness and brightness when being used for treating the ground calcium carbonate powder, and is a high-performance ground calcium carbonate powder fluorescent whitening agent.
Description
Technical Field
The invention relates to the technical field of fluorescent whitening agents, in particular to a pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, and a preparation method and application thereof.
Background
In the development planning of 'twelve five' new materials, new materials which are developed and coordinated with resources and environment are used as main assessment indexes in China, and the problem of resource shortage is solved by developing the new materials. China forms a relatively perfect material science and technology system, has obvious resource advantages and technical advantages in the field of certain new materials, but has relatively weak overall independent innovation capability, has relatively few new material products and technologies with independent intellectual property rights, and is particularly insufficient in innovation in the aspect of the ground limestone powder fluorescent whitening material.
The fluorescent whitening agent has high light quantum yield, and can effectively whiten and brighten the processed substrate. Fluorescent whitening agent molecules have a large conjugated system, can absorb ultraviolet light with the wavelength range of about 300-400 nm and emit blue fluorescent light with the wavelength range of about 420-450 nm, so that visual yellowing caused by blue light deficiency in a matrix is compensated. People feel brighter and brighter substrates treated by compensating blue light. Fluorescent whitening agents are widely used in many fields such as paper making, textiles, detergents, plastics, inks, leather, ultraviolet absorbers, developers and the like, and the market demand is huge.
The heavy calcium carbonate is used as the largest inorganic filler, and is widely applied to the fillers or raw materials of products such as cable materials, synthetic leather, polyethylene films, foamed plastics, plastic pipes, paper and the like due to the advantages of wide raw materials, low price, no toxicity and the like. The heavy calcium carbonate powder is used as a maximum filling material, people have higher requirements on whiteness and brightness, and a plurality of special fluorescent whitening agents for plastics, papermaking, detergents and the like are available in the market, but the heavy calcium carbonate powder fluorescent whitening agents are rare, so that the market demand is very urgent and great.
Free calcium ions and hydroxyl groups are arranged on the surface of the heavy calcium carbonate powder, and the existing fluorescent whitening agent on the market is difficult to be ionically bonded or adsorbed on the surface of the heavy calcium carbonate powder, so that the fluorescent whitening agent capable of effectively whitening and brightening the heavy calcium carbonate powder is lacked.
Disclosure of Invention
Aiming at the defects, the invention aims to provide the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, and the preparation method and the application thereof. By testing the optical performance of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, the fact that the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent has strong ultraviolet absorption performance can be obviously seen. The pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent has stronger bonding force and obvious whitening and brightening effects on heavy calcium carbonate powder. The pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent is a novel high-performance heavy calcium carbonate powder fluorescent whitening agent, and has great popularization and application space.
Specifically, the scheme of the invention is as follows: a pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent has a structural formula shown in formula 1:
meanwhile, the invention also discloses a preparation method of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, which comprises the following steps:
step 1: adding 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution into 2, 4-dichloropyrimidine solution, and adding 10% Na2CO3P of aqueous maintenance systemH value is 7-8, and stirring and reacting for a period of time at 20-25 ℃;
step 2: dimethyltetradecyltriethylamine was then added to the reaction mixture of step 1 over 10% Na2CO3Maintaining the pH value of the system to be 8-9 by using an aqueous solution, and carrying out reflux reaction for a period of time;
and step 3: cooling the reaction mixture to room temperature, adding inorganic salt to separate out and collect the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent;
wherein the mass ratios of the 4,4 '-diaminostilbene-2, 2' -disulfonic acid, the 2, 4-dichloropyrimidine and the dimethyltetradecyl tertiary amine are as follows: 1:2.1:1.95.
In the preparation method of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, in the step 1, 10-15 mL of dimethylformamide corresponds to 10mmol of 2, 4-dichloropyrimidine in the 2, 4-dichloropyrimidine solution; in the 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution, 50-55 mL of water is added to every 5mmol of 4,4 '-diaminostilbene-2, 2' -disulfonic acid.
In the preparation method of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, the pH value of the 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution is 5-6.
In the preparation method of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, the pH value is 10 percent Na2CO3Regulating and controlling the aqueous solution.
In the preparation method of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, the reaction time in the step 1 is 10-11 hours; the reaction time of the step 2 is 6-7 hours.
In the preparation method of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, the inorganic salt in the step 3 is sodium chloride.
In the preparation method of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent, in the step 1, the 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution is added into the 2, 4-dichloropyrimidine solution in a dropwise manner.
In addition, the invention also provides application of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent for whitening and brightening ground calcium carbonate powder.
Compared with the traditional method, the method has the following advantages:
1. the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent disclosed by the invention is simple in synthesis method and low in raw material price.
2. The pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent can be effectively chemically bonded with ions on the surface of heavy calcium carbonate powder, and has high bonding firmness and better weather resistance;
3. the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent has stronger ultraviolet absorption performance, can obviously whiten and brighten heavy calcium carbonate powder, and is a novel high-performance fluorescent whitening agent.
Drawings
FIG. 1 is a UV absorption spectrum of an optical property test of an aqueous solution of a pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent of example 3.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following claims are hereby incorporated into the detailed description of the invention, with the understanding that the present disclosure is to be considered as a full and non-limiting example, and any modifications and variations that fall within the spirit and scope of the claims are intended to be included therein.
Example 1
21mmol of 2, 4-dichloropyrimidine was added to 22mL of dimethylformamide and stirred at 25 ℃. Then, a mixture of 10mmol of 4,4 '-diaminostilbene-2, 2' -disulfonic acid and 100mL of distilled water was added dropwise thereto, followed by addition of 10% Na2CO3The reaction was carried out at 25 ℃ for 11 hours while maintaining the pH of the reaction system at 7 in an aqueous solution. Then 19.5mmol of dimethyltetradecylamine and 10% Na are added2CO3The aqueous solution was maintained at pH 9 and the reaction was refluxed for 7 h. The two-step reaction endpoint was monitored by thin layer chromatography. Cooling to room temperature, adding 20g of sodium chloride, stirring, carrying out suction filtration, and carrying out vacuum drying to obtain the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent with the yield of 87%.
Example 2
21mmol of 2, 4-dichloropyrimidine was added to 31.5mL of dimethylformamide and stirred at 20 ℃. Then 10mmol of 4,4 '-diaminostilbene-2, 2' - -Mixture of disulfonic acid and 110mL of distilled water with 10% Na2CO3The reaction was carried out at 25 ℃ for 10 hours while maintaining the pH of the reaction system at 8 in an aqueous solution. Then 19.5mmol of dimethyltetradecylamine and 10% Na are added2CO3The aqueous solution was maintained at pH 8 and the reaction was refluxed for 6 h. The two-step reaction endpoint was monitored by thin layer chromatography. Cooling to room temperature, adding 20g of sodium chloride, stirring, filtering, and vacuum drying to obtain the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent with the yield of 83%.
Example 3
21mmol of 2, 4-dichloropyrimidine was added to 26mL of dimethylformamide and stirred at 25 ℃. Then, a mixture of 10mmol of 4,4 '-diaminostilbene-2, 2' -disulfonic acid and 100mL of distilled water was added dropwise thereto, followed by addition of 10% Na2CO3The reaction was carried out at 25 ℃ for 11 hours while maintaining the pH of the reaction system at 7.5 in an aqueous solution. Then 19.5mmol of dimethyltetradecylamine and 10% Na are added2CO3The aqueous solution was maintained at pH 9 and the reaction was refluxed for 7 h. The two-step reaction endpoint was monitored by thin layer chromatography. Cooling to room temperature, adding 20g of sodium chloride, stirring, filtering, and vacuum drying to obtain the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent with the yield of 84.5%.
Optical Performance testing
The product of the invention is subjected to optical performance test by adopting an ultraviolet-visible spectrum, and an ultraviolet absorption spectrogram is shown in figure 1.
The uv-vis spectrum can effectively test the conjugated systems of the fluorescent whitening agent molecules. The pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent is prepared into an aqueous solution with the concentration of 0.02g/L for optical performance test. The test result shows that the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent has stronger ultraviolet absorption performance, and the maximum absorption peak is located at 346 nm.
Whitening Performance test
100mL of aqueous solution with the mass concentration of 0.01-0.03% of pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent is prepared, and 100g of ground calcium carbonate powder with different particle sizes and whiteness is treated. The method comprises the following steps: and (3) putting the heavy calcium carbonate powder with different particle sizes and whiteness into a proper amount of solution with the concentration, stirring for 30min at room temperature, draining, and drying to obtain the high-whiteness and high-brightness heavy calcium carbonate powder.
Experimental results prove that the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent has remarkable whitening and brightening effects on calcium carbonate powder with different qualities, and when the concentration is 0.02%, heavy calcium carbonate powder with the granularity of 400-2500 meshes and the whiteness of 91-95 is treated, and the whiteness increase value is between 1 and 2.5. The pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent is a novel high-performance ground calcium carbonate powder fluorescent whitening agent, and has great popularization and application space.
The above description is only exemplary of the invention, and any modification, equivalent replacement, and improvement made within the spirit and scope of the present invention should be considered within the scope of the present invention.
Claims (3)
2. a process for the preparation of a pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent according to claim 1, which comprises the following steps:
(1) adding 4,4 '-diaminostilbene-2, 2' -disulfonic acid aqueous solution into 2, 4-dichloropyrimidine solution, and adding 10% Na2CO3Maintaining the pH value of the system to be 7-8 by using the aqueous solution, and stirring and reacting for 10-11 hours at the temperature of 20-25 ℃;
(2) dimethyltetradecyltriethylamine was added to the reaction mixture of step 1 over 10% Na2CO3Maintaining the pH value of the system to be 8-9 by using the aqueous solution, and carrying out reflux reaction for 6-7 hours;
(3) cooling the reaction mixture to room temperature, adding inorganic salt to separate out and collect the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent;
wherein the mass ratio of the 4,4 '-diaminostilbene-2, 2' -disulfonic acid, the 2, 4-dichloropyrimidine and the dimethyltetradecyl tertiary amine is as follows: 1:2.1:1.95.
3. The use of the pyrimidine-tetradecyl quaternary ammonium salt fluorescent whitening agent as claimed in claim 1, is characterized in that the fluorescent whitening agent is used for whitening and brightening ground calcium carbonate powder.
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WO2000046336A1 (en) * | 1999-02-05 | 2000-08-10 | Ciba Specialty Chemicals Holding Inc. | Fluorescent whitening agent, its preparation and use |
CN102504570A (en) * | 2011-09-26 | 2012-06-20 | 山东大学 | Fluorescent whitening agent with di-ethers quaternary ammonium salt and synthesis and application thereof |
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WO2000046336A1 (en) * | 1999-02-05 | 2000-08-10 | Ciba Specialty Chemicals Holding Inc. | Fluorescent whitening agent, its preparation and use |
CN102504570A (en) * | 2011-09-26 | 2012-06-20 | 山东大学 | Fluorescent whitening agent with di-ethers quaternary ammonium salt and synthesis and application thereof |
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