CN109134723B - Method for polymerizing stilbene disazo dye - Google Patents
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- CN109134723B CN109134723B CN201810412053.2A CN201810412053A CN109134723B CN 109134723 B CN109134723 B CN 109134723B CN 201810412053 A CN201810412053 A CN 201810412053A CN 109134723 B CN109134723 B CN 109134723B
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- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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Abstract
The invention relates to a method for polymerizing stilbene disazo dye. The tertiary amine can generate redox reaction with potassium persulfate at normal temperature to generate active free radicals for many times, oil-soluble monomer vinyl acetate is initiated to polymerize on a water/oil interface, and the obtained product is hydrolyzed to obtain a polymer containing a hydrophilic polyvinyl alcohol chain segment, so that the aim of realizing the high polymerization of the stilbene disazo dye is fulfilled.
Description
Technical Field
The invention relates to the technical field of synthesis of functional polymer materials, in particular to a high-molecular preparation technology of stilbene disazo dye.
Background
Polyolefin is a very important general high molecular material, is formed by free radical polymerization of a plurality of olefin monomers, and is widely applied by realizing adjustable structure according to monomer copolymerization technology aiming at different purposes. The initiator is indispensable in the preparation of high polymer materials, the common initiator is a compound capable of generating free radicals, such as oil-soluble peroxy initiators, azo initiators, water-soluble persulfate and the like, the use of the initiator must be matched with a specific polymerization reaction environment, conventionally, one initiator only corresponds to a certain polymerization reaction, and the structure and the function of the initiator are relatively simple. If the structure and the function of the initiator are designed and modified, the free radical polymerization reaction can completely play a stronger role, and the obtained polymer material has higher application value.
The direct yellow G is a direct dye with a stilbene disazo structure, contains hydrophilic sulfonic acid groups, is orange powder in appearance, is dissolved in water to form a golden yellow solution, and is called as the yellow when a water solution is lower than 15 ℃ and a frozen precipitate is separated out. The dye has strong dyeing power and is lightfast, is a valuable yellow dye in the textile industry, is mainly used for dyeing cellulosic fiber fabrics such as cotton, hemp, viscose, rayon and rayon, dyeing fabrics such as silk, chinlon and the like and the blended fabrics thereof, and can also be used for dyeing leather, paper pulp and biology and manufacturing lakes and pigments. The azo dye is introduced into a macromolecular structure to form the macromolecular dye, is more stable than a micromolecular dye, is not easy to fall off, and is more easy to be compounded with other materials, so that the azo dye has wider application value. One modification is to convert the dye molecule into a polymerizable monomer and copolymerize it with other olefin monomers, but this method is costly, prone to affect critical polymerization reactions, and has poor flexibility and diversity.
The solution of the invention is to prepare the functional polymer by taking the development of the functional initiator as a basic starting point, rather than modifying the functional molecule into a monomer, so that the advantages of the invention are that the functionalization and the polymerization reaction are not interfered with each other, and the adaptability and the operability are greatly improved. The key point of the invention is to obtain the functional initiator shown in figure 1, which not only contains functional stilbene bisazo radical, but also has the characteristics of amphipathy of water and oil, and can be positioned at the interface of water phase and oil phase, so that the generated free radical can polymerize monomers in the water phase and monomers in the oil phase, the limitation of high molecular weight is broken, various functional polymers can be obtained by changing the types of the monomers, the high molecular weight range is greatly expanded, and the functional initiator can be more suitable for various application requirements.
The initiator provided by the invention utilizes redox reaction to generate free radicals, the mechanism of initiating polymerization reaction is shown in figure 2, wherein the reducing agent is an organic tertiary amine structure, and the oxidizing agent is added water-soluble K2S2O8The initiator alone does not have an initiating function, once it is reacted with K2S2O8Put together and can take place redox reaction at room temperature, the nitrogen atom loses an electron and becomes cation free radical, then ionize the hydrogen ion on the adjacent carbon atom through intramolecular charge transfer, form the carbon free radical, the nitrogen atom can also be oxidized repeatedly after being reduced, until the hydrogen atom on the adjacent carbon atom is totally replaced, so this kind of initiating agent can produce free radical many times. The generated interfacial free radicals can initiate polymerization reaction of an oil phase and polymerization reaction of a water phase, the dilution degree of functional molecules can be adjusted by controlling the dosage of monomers, and the polymerization mode has very large degree of freedom, so that the method has very strong adaptability and is really high-molecular. And the polymerization mode completely meets the standard of green chemistry, namely low energy consumption of normal-temperature reaction, no organic solvent and no other surfactant.
On the other hand, the invention can lead the stilbene tetrazo functional molecule to be introduced into various high molecular materials, and lead the stilbene tetrazo molecule to be dispersed in a high molecular matrix in a molecular form, thereby thoroughly solving the problem of easy association and aggregation of the stilbene tetrazo functional molecule, greatly improving the processability of the functional high molecule, greatly reducing the using amount of the stilbene tetrazo dye and strictly avoiding the possibility that the functional materials can cause pollution to the environment.
Disclosure of Invention
The invention provides a method for polymerizing stilbene disazo dye, which is characterized in that firstly an amphiphilic initiator containing stilbene disazo functional groups is synthesized, then water-soluble or oil-soluble monomer polymerization is initiated at a water/oil phase interface by utilizing free radicals generated by redox reaction of the initiator and potassium persulfate at normal temperature, and finally a functional polymer containing stilbene disazo groups is formed.
Another technical problem to be solved by the present invention is to provide a method for preparing the above functional initiator, which is practical, simple and convenient to operate, and easy for mass preparation.
The invention aims to solve the technical problem of providing a specific application of the functional initiator in preparing high polymer materials by polymerizing olefin monomers.
1. The technical scheme adopted by the invention for solving the primary technical problem is as follows: an amphiphilic initiator containing stilbene tetrazo functional groups has a chemical structure shown in figure 1, is a functional surfactant, and can generate active free radicals for many times under the oxidation action of potassium persulfate to initiate the polymerization of oily or aqueous olefin monomers, so that the aim of realizing the high polymerization of stilbene tetrazo dyes is fulfilled.
The method has the advantages that two operations of functionalization and polymerization are not interfered with each other, the adaptability and the operation freedom degree of the method are greatly improved, and the stilbene tetrazo molecules can be introduced into various high polymer materials by one initiator;
the method has the advantages that the tertiary amine structure in the initiator can react with potassium persulfate at normal temperature, active free radicals can be generated on alpha-carbon for multiple times through continuous nitrogen oxide atoms, aqueous or oily monomer polymerization can be initiated in a two-way manner, and other solvents and emulsifiers are not required to be added;
the method has the advantages that the content of the stilbene tetrazo unit in the polymer material can be adjusted by controlling the using amount of the monomer, the problem that stilbene tetrazo molecules are easy to associate and aggregate is thoroughly solved, the processability of functional polymers is improved, and the macromolecular stilbene tetrazo dye can be used for paint, ink and dye matrix to dye polymer fiber materials.
2. The technical scheme adopted by the invention for solving another technical problem is as follows: the preparation method of the functional initiator has a synthetic route shown in figure 3, and is characterized by comprising the following steps: 1) dissolving 0.1mol of stilbene bisazo phenol in 400ml of water, adding 0.2mol of NaOH, gradually adding 0.2mol of epoxy chloropropane under stirring, controlling the temperature of a reaction solution to be within a range of 50-55 ℃, reacting for 3-4 hours, adding 0.22mol of ethanolamine after the reaction is finished, continuing reacting for 2-3 hours at a temperature of 30-35 ℃, acidifying with hydrochloric acid until the pH value is within a range of 4.0-4.5, generating a large amount of yellow precipitates, collecting precipitates, washing with clear water for multiple times, filtering, and drying in vacuum; 2) dissolving the product obtained in the last step in 300ml of absolute ethanol, adding 0.2mol of isooctyl glycidyl ether and 0.2mol of NaOH solid under stirring, continuously stirring for 4-5 hours at the temperature of 25-30 ℃ to obtain golden homogeneous reaction liquid, concentrating by using a rotary evaporator to remove ethanol, and finally obtaining yellow solid matter.
3. The technical scheme adopted by the invention for solving the other technical problem is as follows: the use method of the functional initiator in polymerization reaction is characterized by comprising the following steps: 1) dispersing 18.0g of functional initiator in 800mL of water to prepare an emulsion, wherein the concentration is controlled to be within the range of 2.0-2.5 wt.%; 2) adding oil-soluble monomer vinyl acetate into emulsion, wherein the weight ratio of the monomer to the initiator is 1: 1-4: 1, fully stirring, adding potassium persulfate solid powder, the using amount of which is 2.0-3.0% of the weight of the initiator, carrying out polymerization reaction after 5-10 minutes, raising the system temperature, quickly forming yellow polymer particles, wherein the color of the water phase can hardly be seen, completing the polymerization reaction within 1-2 hours, and collecting particles, namely hydrophobic stilbene bisazo dye high-molecular products; 3) and after the second step is finished, dissolving the obtained polymer in methanol, keeping the concentration of the polymer within the range of 10-15 g/100ml, adding NaOH solid accounting for 5-7% of the weight of the polymer, refluxing for 2-3 hours under stirring, separating out the polymer in yellow precipitate after the reaction is finished, filtering, washing with clear water, and drying in vacuum, wherein the obtained yellow solid matter contains a polyvinyl alcohol chain segment, and the obtained yellow solid matter is a hydrophilic stilbene disazo dye high-molecular product.
The polymerization reaction has high speed and high conversion rate, and the monomer can be gradually added in the polymerization process, so that the reaction temperature is convenient to control;
it is very beneficial that no other organic solvent is added in the whole polymerization process, no harsh conditions are needed, and the requirements of green chemistry are completely met.
The invention has the advantages that: 1) the functionalization and the polymerization reaction are not interfered with each other, and the operation freedom degree is large; 2) one initiator can be used for preparing various functional polymers, and the adaptability is strong; 3) the polymerization reaction condition is mild and controllable, the energy consumption is low, other organic solvents and emulsifiers are not used, the product is pure, and the requirements of green chemistry are met.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation of functional initiator:
stilbene bisazo phenol is used as a starting material, which is already commercially available, so that the preparation thereof is a ready-made process, which is not repeated here, the following being the specific preparation steps:
1) dissolving 0.1mol of stilbene bisazo phenol in 400ml of water, adding 0.2mol of NaOH, gradually adding 0.2mol of epoxy chloropropane under stirring, controlling the temperature of a reaction solution to be within a range of 50-55 ℃, reacting for 3-4 hours, adding 0.22mol of ethanolamine after the reaction is finished, continuing reacting for 2-3 hours at a temperature of 30-35 ℃, acidifying with hydrochloric acid until the pH value is within a range of 4.0-4.5, generating a large amount of yellow precipitates, collecting precipitates, washing with clear water for multiple times, filtering, and drying in vacuum;
2) dissolving the product obtained in the last step in 300ml of absolute ethanol, adding 0.2mol of isooctyl glycidyl ether and 0.2mol of NaOH solid under stirring, continuously stirring for 4-5 hours at the temperature of 25-30 ℃ to obtain golden homogeneous reaction liquid, concentrating by using a rotary evaporator to remove ethanol, and finally obtaining yellow solid matter.
The use method of the functional initiator comprises the following steps:
the vinyl acetate is taken as a representative of oil-soluble monomers, the oil-soluble polyvinyl alcohol copolymer has the characteristics of hydrophilicity and lipophilicity, the obtained polymer is further hydrolyzed to obtain a water-soluble high polymer product taking polyvinyl alcohol as a chain segment, and the specific polymerization reaction is carried out according to the following operation steps:
1) dispersing 18.0g of functional initiator in 800mL of water to prepare an emulsion, wherein the concentration is controlled to be within the range of 2.0-2.5 wt.%;
2) respectively adding 18g, 36g, 54g and 72g of monomer vinyl acetate into emulsion of different batches for multiple parallel tests, adding potassium persulfate solid powder after fully stirring, wherein the dosage of the potassium persulfate solid powder is 2.0-3.0% of the weight of the added functional initiator, carrying out polymerization reaction after 5-10 minutes, wherein the system temperature can be increased from 15-20 ℃ to about 40-45 ℃, quickly forming yellow polymer particles, finishing the polymerization reaction within 1-2 hours, almost no color exists in the water phase, and collecting the particles, namely hydrophobic stilbene bisazo dye high molecular products;
3) and after the second step is finished, dissolving the obtained polymer in methanol, keeping the concentration of the polymer within the range of 10-15 g/100ml, adding NaOH solid accounting for 5-7% of the weight of the polymer, refluxing for 2-3 hours under stirring, separating out the polymer in yellow precipitate after the reaction is finished, filtering, washing with clear water, and drying in vacuum, wherein the obtained yellow solid matter contains a polyvinyl alcohol chain segment, and the obtained yellow solid matter is a hydrophilic stilbene disazo dye high-molecular product.
Component analysis of the high-molecular product:
the polymer mainly comprises two structures, one is a chain segment after the polymerization of the olefin monomer, the other is the initiator itself, the mass ratio of the two structures can be analyzed by the absorbance, 1g of the initiator is dissolved in 100ml of the solvent, the absorbance is measured to be A1, then 1g of the polymer sample is dissolved in 100ml of the solvent, the absorbance is measured to be A2, the maximum absorption wavelength is the same because of the same light absorption groups, and the obtained result has the relation that the M/I is A1/A2-1, where M/I is the ratio of the mass of the polymerized segment to the mass of the initiator in the sample, this value should be dependent on the ratio of the mass of monomer to the mass of initiator in the polymerization reaction, the closer these two values are, the more complete the polymerization is. The results of the experiments are summarized in FIG. 4, which shows the M/I and M/I mapping bases in generalThis is a diagonal line, indicating that the conversion of the monomer is relatively high and the effect of polymerization is relatively satisfactory.
Description of the method of use:
the functional initiator is characterized in that the dosage of the functional initiator far exceeds that of a common initiator in the using process, and the dosage of the initiator is 20-100% of the weight of a monomer, because the initiator is not an initiator in the common sense, the purpose of the initiator is not only to initiate polymerization reaction, but also to introduce functional groups, so that the functional components are ensured to occupy certain specific gravity in the material, and if the specific gravity is too low, the functional materials cannot be called as the functional materials. This specific gravity can be adjusted according to the specific application.
Drawings
FIG. 1 chemical structure of a functional initiator.
FIG. 2 shows the principle of redox-initiated two-phase polymerization of oil and water.
FIG. 3 scheme for the synthesis of functional initiators.
FIG. 4 shows the relationship between the composition of the polymer material and the charge ratio.
Claims (1)
1. A method for polymerizing stilbene disazo dye is characterized in that a functional initiator with the following structure is used:
the operation steps of the high molecular method are as follows in sequence:
1) dispersing 18.0g of functional initiator in 800mL of water to form an emulsion;
2) adding oil-soluble monomer vinyl acetate into the emulsion, wherein the weight ratio of the monomer to the initiator is 1: 1-4: 1; after fully stirring, adding potassium persulfate solid powder, the dosage of which is 2.0-3.0% of the weight of the added initiator, wherein after 5-10 minutes, a polymerization reaction occurs, the system temperature rises to some extent, colored polymer particles are quickly formed, the polymerization reaction is completed within 1-2 hours, the color can not be seen in a water phase, and the collected particles are hydrophobic stilbene bisazo dye high-molecular products;
3) and 2) dissolving the obtained polymer in methanol after the step 2), keeping the concentration of the polymer in a range of 10-15 g/100ml, adding NaOH solid accounting for 5-7% of the weight of the polymer, refluxing for 2-3 hours under stirring, separating out the polymer in yellow precipitate after the reaction is finished, filtering, washing with clear water, and drying in vacuum, wherein the obtained yellow solid matter contains a polyvinyl alcohol chain segment, and the obtained yellow solid matter is a hydrophilic stilbene disazo dye high-molecular product.
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