CN109134770B - High-molecular method of active brilliant red dye K-2BP - Google Patents
High-molecular method of active brilliant red dye K-2BP Download PDFInfo
- Publication number
- CN109134770B CN109134770B CN201810412051.3A CN201810412051A CN109134770B CN 109134770 B CN109134770 B CN 109134770B CN 201810412051 A CN201810412051 A CN 201810412051A CN 109134770 B CN109134770 B CN 109134770B
- Authority
- CN
- China
- Prior art keywords
- initiator
- polymerization reaction
- functional
- dye
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a high molecular method of reactive brilliant red K-2BP dye. An amphiphilic compound containing an active bright red group and a tertiary amine structure is synthesized and can be used as an initiator of free radical polymerization, the tertiary amine can perform redox reaction with potassium persulfate at normal temperature to generate active free radicals for many times, and can initiate polymerization of oil-soluble monomer butyl acrylate and water-soluble monomer dimethyl diallyl ammonium chloride on a water/oil interface, so that the aim of high polymerization of the active bright red K-2BP 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 reactive brilliant red 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 reactive dye has a reactive group which can react with a functional group on the fiber, so that dye molecules are connected with a material main body through chemical bonds, and dyeing is more stable. The reactive brilliant red K-2BP is a dye obtained by condensing H acid and cyanuric chloride, coupling with diazo o-aminobenzenesulfonate and condensing with o-chloroaniline, is mainly used for printing hemp, cotton and viscose fabrics, and has good fastness to sunlight, weather, washing and soaping, but poor discharge property. 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 active bright red groups, 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 radicals 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, and the high molecular weight range is greatly expanded, thereby being 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 K2S2O8The oxidation-reduction reaction can be carried out at normal temperature when the materials are put together,the nitrogen atom loses one electron to become a cation free radical, then hydrogen ions are ionized on adjacent carbon atoms through intramolecular charge transfer to form a carbon free radical, and the nitrogen atom can be repeatedly oxidized after being reduced until the hydrogen atoms on the adjacent carbon atoms are completely replaced, so that the initiator can generate the free radical for 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 introduce the active bright red functional molecules into various high molecular materials, so that the active bright red molecules can be dispersed in a high molecular matrix in a molecular form, thereby thoroughly solving the problem of easy association and aggregation of the active bright red molecules, greatly improving the processability of the functional high molecules, greatly reducing the consumption of the active bright red dye and strictly avoiding the possibility of environmental pollution caused by the functional materials.
Disclosure of Invention
The invention provides a method for polymerizing reactive brilliant red dye, which is characterized in that firstly an amphiphilic initiator containing reactive brilliant red 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 the reactive brilliant red 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 reactive brilliant red functional groups has a chemical structure shown in figure 1, is a functional surfactant, and can generate reactive free radicals for many times under the oxidation action of potassium persulfate to initiate the polymerization of oily or aqueous olefin monomers, thereby realizing the purpose of high polymerization of reactive brilliant red dyes.
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 active bright red 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 reactive brilliant red units in the polymer material can be adjusted by controlling the using amount of the monomers, the problem that the reactive brilliant red molecules are easy to associate and aggregate is thoroughly solved, the processability of the functional polymer is improved, and the high-molecular reactive brilliant red dye can be used for coating, printing ink and used as a 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 reactive brilliant red K-2BP in 400ml of water, gradually adding 0.3mol of NaOH while stirring, then adding 0.1mol of ethylenediamine, controlling the temperature of a reaction solution to be within a range of 40-45 ℃, reacting for 3-4 hours, and evaporating most of water by using a rotary evaporator after the reaction is finished; 2) adding 200ml of absolute ethyl alcohol into the residue obtained in the previous step, adding 0.2mol of isooctyl glycidyl ether under stirring, continuously stirring for 4-5 hours at the temperature of 55-60 ℃ to obtain a purple homogeneous reaction liquid, and concentrating by using a rotary evaporator to remove the ethyl alcohol and water to finally obtain a purple solid substance, wherein the product is the functional initiator containing active bright red groups and can be well dispersed in water.
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 15.0g of functional initiator in 800mL of water to prepare an emulsion, wherein the concentration is controlled to be 1.5-2.0 wt.%; 2) adding oil-soluble monomer butyl acrylate 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, after 5-10 minutes, carrying out polymerization reaction, raising the system temperature to a certain extent, quickly forming colored polymer particles, completing the polymerization reaction within 1-2 hours, wherein the color can not be seen in a water phase, and the collected particles are hydrophobic active bright red dye high-molecular products; 3) after the first step is finished, adding 50 wt.% of dimethyl diallyl ammonium chloride aqueous solution into the 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 still 2.0-3.0% of the weight of the added functional initiator, starting the polymerization reaction after 10-15 minutes, raising the system temperature to some extent, gradually enabling the red reaction system to become very viscous, finishing the polymerization reaction after 1.5-2.5 hours, and drying the finally obtained solution to obtain a red solid substance, namely the high molecular product of the hydrophilic reactive bright red dye.
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:
the reactive brilliant red K-2BP is used as a starting material, which is already commercialized, so that the preparation method thereof is ready to use and is not repeated here, and the following are specific preparation steps:
1) dissolving 0.1mol of reactive brilliant red K-2BP in 400ml of water, gradually adding 0.3mol of NaOH while stirring, then adding 0.1mol of ethylenediamine, controlling the temperature of a reaction solution to be within a range of 40-45 ℃, reacting for 3-4 hours, and evaporating most of water by using a rotary evaporator after the reaction is finished;
2) adding 200ml of absolute ethyl alcohol into the residue obtained in the previous step, adding 0.2mol of isooctyl glycidyl ether under stirring, continuously stirring for 4-5 hours at the temperature of 55-60 ℃ to obtain a purple homogeneous reaction liquid, and concentrating by using a rotary evaporator to remove the ethyl alcohol and water to finally obtain a purple solid substance, wherein the product is the functional initiator containing active bright red groups and can be well dispersed in water.
The use method of the functional initiator comprises the following steps:
butyl acrylate is taken as a representative of a lipophilic monomer, dimethyl diallyl ammonium chloride is taken as a representative of a cationic monomer, and the specific polymerization reaction is carried out according to the following operation steps:
1) dispersing 15.0g of functional initiator in 800mL of water to prepare an emulsion, wherein the concentration is controlled to be 1.5-2.0 wt.%;
2) respectively adding 15g, 30g, 45g and 60g of monomer butyl acrylate into emulsions 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 red polymer particles, finishing the polymerization reaction within 1-2 hours, almost no color exists in the water phase, and the collected particles are high molecular products of hydrophobic reactive bright red nitrogen dyes;
3) after the first step is finished, respectively adding 30g, 60g, 90g and 120g of dimethyl diallyl ammonium chloride aqueous solution (50 wt.%) into emulsions of different batches for multiple parallel tests, then adding potassium persulfate solid powder, wherein the dosage of the potassium persulfate solid powder is still 2.0-3.0% of the weight of the added functional initiator, starting the polymerization reaction after 10-15 minutes, raising the temperature of the system to a certain extent, gradually making the red reaction system become very viscous, finishing the polymerization reaction after 1.5-2.5 hours, and finally drying the obtained solution to obtain a red solid substance, namely the high molecular product of the hydrophilic reactive bright red dye.
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, the mass ratio of the two structures can be analyzed by absorbance, 1g of the initiator is dissolved in 100ml of solvent, and the absorbance is measured to be A1Then, 1g of the polymer sample was dissolved in 100ml of a solvent, and the absorbance was measured as A2Since the absorption groups are the same, the absorption maximum wavelength is the same, and the result is obtained with the relation M/I ═ 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, and the M/I and M/I are plotted substantially near the diagonal line in general, which shows that the conversion rate of the monomer is relatively high and the effect of high molecular weight 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 reactive brilliant red 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 15.0g of functional initiator in 800mL of water to form an emulsion;
2) adding an oil-soluble butyl acrylate monomer into the emulsion, wherein the weight ratio of the monomer to an 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, after 5-10 minutes, carrying out polymerization reaction, raising the system temperature to a certain extent, quickly forming colored polymer particles, completing the polymerization reaction within 1-2 hours, wherein the color can not be seen in a water phase, and the collected particles are hydrophobic active bright red dye high-molecular products;
or after the step 1) is finished, adding 50 wt.% of dimethyl diallyl ammonium chloride aqueous solution into the 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 still 2.0-3.0% of the weight of the added functional initiator, starting the polymerization reaction after 10-15 minutes, raising the system temperature, gradually making the red reaction system become very viscous, finishing the polymerization reaction after 1.5-2.5 hours, and drying the obtained solution to obtain a red solid substance, namely the high molecular product of the hydrophilic reactive bright red dye.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412051.3A CN109134770B (en) | 2018-04-18 | 2018-04-18 | High-molecular method of active brilliant red dye K-2BP |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412051.3A CN109134770B (en) | 2018-04-18 | 2018-04-18 | High-molecular method of active brilliant red dye K-2BP |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134770A CN109134770A (en) | 2019-01-04 |
| CN109134770B true CN109134770B (en) | 2021-09-21 |
Family
ID=64801666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810412051.3A Active CN109134770B (en) | 2018-04-18 | 2018-04-18 | High-molecular method of active brilliant red dye K-2BP |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134770B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912731B (en) * | 2019-02-27 | 2021-11-16 | 宁波大学 | Non-ionic dihydrazide initiator and preparation and use method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820273A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini cationic surface active initiator and preparation method thereof |
| CN105884937A (en) * | 2015-06-12 | 2016-08-24 | 宁波大学 | Anionic surface active initiator and preparation method thereof |
| CN106496398A (en) * | 2016-10-22 | 2017-03-15 | 宁波大学 | A kind of environment-friendly preparation method thereof of cationic polyvinylidene fluoride film material |
-
2018
- 2018-04-18 CN CN201810412051.3A patent/CN109134770B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884937A (en) * | 2015-06-12 | 2016-08-24 | 宁波大学 | Anionic surface active initiator and preparation method thereof |
| CN105820273A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini cationic surface active initiator and preparation method thereof |
| CN106496398A (en) * | 2016-10-22 | 2017-03-15 | 宁波大学 | A kind of environment-friendly preparation method thereof of cationic polyvinylidene fluoride film material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109134770A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106317285B (en) | A kind of waterborne pigment dispersant | |
| CN112062918B (en) | Method for synthesizing polymer/pigment hybrid latex by copolymerization of sulfur-free and soap-free in-situ RAFT (reversible addition-fragmentation chain transfer) emulsion | |
| CN101186672B (en) | Water solution polymerization preparation method for dimethyl diallyl ammonium chloride and acrylamide copolymers | |
| DE4034642A1 (en) | WATER-SOLUBLE MIXED POLYMERS AND THEIR USE | |
| CN101775099A (en) | Paint thickener for printing and preparation method thereof | |
| CN110499218B (en) | Efficient environment-friendly acid soaping agent and preparation method thereof | |
| CN104817663A (en) | Preparation method of polycarboxylate water-reducer capable of inhibiting side-effect of montmorillonite and polymeric monomer | |
| CN102433107A (en) | Low-molecular-weight polymer type filtrate loss reducer for drilling fluid and preparation method for same | |
| CN109134769B (en) | High-molecular method of perylene bisimide fluorescent dye | |
| CN109134770B (en) | High-molecular method of active brilliant red dye K-2BP | |
| CN114736659A (en) | Preparation method of high-temperature high-density water-based drilling fluid filtrate reducer composition | |
| CN111138612A (en) | Printing thickener and preparation method thereof | |
| CN105085838A (en) | Preparation method of modified nanometer SiO2-AA-AM copolymer | |
| CN109134723B (en) | Method for polymerizing stilbene disazo dye | |
| CN103254365A (en) | Method for preparing ASA (Acrylonitrile-Styrene-Acrylate) copolymer latex by using water-solubility redox initiator at low temperature | |
| CN109134774B (en) | High-molecular method of reactive black dye KN-B | |
| CN103936941A (en) | Amphiphilic core-shell emulsion adhesive for pigment printing of textile and preparation method thereof | |
| CN109134773B (en) | High-molecular method of fluorescein dye | |
| CN109134766B (en) | High-molecular method of naphthalimide fluorescent dye | |
| CN109134726B (en) | Phthalocyanine dye high-molecular method | |
| CN109134735B (en) | High-molecular method of disperse scarlet dye S-BWFL | |
| CN108484839A (en) | A kind of amphipathic carboxylic dispersants and preparation method thereof | |
| CN105085837A (en) | Modified nanometer SiO2-AA-AM copolymer | |
| CN104152131B (en) | A kind of polymer oil-displacing agent containing sulphite structure and synthetic method thereof | |
| CN106317304B (en) | A kind of polymer and its preparation method and application with surface active function |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |