CN109134723A - A kind of producing high-molecular method of talan bisazo dye - Google Patents
A kind of producing high-molecular method of talan bisazo dye Download PDFInfo
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- CN109134723A CN109134723A CN201810412053.2A CN201810412053A CN109134723A CN 109134723 A CN109134723 A CN 109134723A CN 201810412053 A CN201810412053 A CN 201810412053A CN 109134723 A CN109134723 A CN 109134723A
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- 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
- 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
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C—CHEMISTRY; METALLURGY
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- C08F8/00—Chemical modification by after-treatment
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Abstract
The present invention relates to a kind of producing high-molecular methods of talan bisazo dye.Synthesize a kind of amphiphilic compound containing fluorescein base group and tertiary amine structure, the initiator that can be used as free radical polymerization uses, with potassium peroxydisulfate redox reaction can occur for its tertiary amine at normal temperature, repeatedly generate living radical, cause oil-soluble monomer Polymerization of Vac in water/oil interface, products therefrom is obtained to the polymer for containing hydrophilic polyvinyl alcohol segments by hydrolysis, to realize the purpose of talan bisazo dye producing high-molecular, this mode can be such that functionalization does not interfere with each other with polymerization reaction, it is big to operate freedom degree, product species are more, polymeric reaction condition is mild, without organic solvent and emulsifier, meet the requirement of Green Chemistry.
Description
Technical field
The present invention relates to functional polymer material synthesis technical field, especially a kind of height of talan bisazo dye
Talan disazo dye molecule can be introduced polyolefins high score by the new synthetic technology by molecularization technology of preparing
In sub- material, to generate a new class of functional polymer material and its relevant application technology.
Background technique
Polyolefin is a kind of very important commodity polymer material, is to pass through free radical polymerization by several olefinic monomer
And formed, for different purposes, realize that structure is adjustable according to monomer copolymerizable technology, thus be widely used.Initiator is in height
Be in molecular material preparation it is essential, common initiator is a kind of compound that can be generated free radicals, such as oil-soluble
Peroxide, azo-initiator and water-soluble persulfate etc., the use of initiator have to and specific polymerization reaction
Environment matches, and conventionally, a kind of initiator only corresponds to polymerization reaction of certain one kind, and the structure of initiator is opposite with function
For it is fairly simple.If the structure and function of initiator is designed and is transformed, Raolical polymerizable can be made completely
Stronger function is played, polymer material obtained has bigger application value.
Chrysophene G is a kind of direct dyes with talan bisazo structure, containing hydrophilic sulfonic acid group, outside
Sight is crocus powder, and soluble in water is golden yellow to yellow solution, and aqueous solution has jelly shape sediment to be precipitated when being lower than 15 DEG C, therefore
Claim to freeze yellow.Its dyeing capacity is strong, sun-proof, is a kind of valuable weld in textile industry, is mainly used for cotton, fiber crops, viscose glue, people
Cotton, the dyeing of the cellulose base fiber fabrics such as artificial silk, silk, the dyeing of the fabrics such as polyamide fibre and its dyeing of blended fabric are made, also
It can be used for leather, paper pulp, biological dyeing and manufacture color lake, pigment are used.Azo dyes is introduced into macromolecular structure just
As high molecular dye, it is more stable than small molecule dyes, not easily to fall off, it is easier to and it is compound with other materials, thus have
More wide application value.A kind of remodeling method be dye molecule is become to polymerizable monomer, and with other alkene lists
Body is copolymerized, but this method is at high cost, is easy to influence crucial polymerization reaction, adaptability is poor with diversity.
Solution of the invention be prepare functional polymer using development functionality initiator as basic point of departure, and
It is not that functional molecular is transformed into monomer, this have the advantage that functionalization is not interfere with each other with polymerization reaction, substantially increases
Adaptability and operability.Key of the invention is to obtain functional initiator as shown in Figure 1, it not only contains functionality
Talan bisazo groups, and itself have the characteristics that water, oil it is amphiphilic, can be located in water phase with oil phase boundary
Face, in this way caused by free radical can make monomer polymerization in water phase but also make the monomer polymerization in oily phase, producing high-molecular
Limitation be broken, by change monomer type be obtained with various functional polymers, the range of producing high-molecular
It greatly expands, thus is suitable for various application needs.
Initiator provided by the present invention is generated free radicals using redox reaction, the machine of initiated polymerization
For system as shown in Fig. 2, reducing agent therein is trimethylamine structure, oxidant is additional water-soluble K2S2O8, the initiator list
Initiation function is not had in the presence of solely, once by it and K2S2O8Redox reaction can be occurred at normal temperature by putting together,
Nitrogen-atoms loses an electronics and becomes radical cation, is then powered on and is separated out in adjacent carbon atom by Intramolecular electron transfer
Hydrogen ion forms carbon radicals, and nitrogen-atoms can be with repeated oxidation, until the hydrogen atom on adjacent carbon atom is complete after being reduced
Portion replaces, so this initiator can be generated free radicals repeatedly.Generated interface free radical can cause the polymerization of oily phase
Reaction, can also cause the polymerization reaction of water phase, by control monomer dosage can regulatory function molecule dilute strength, this
Kind polymerization methods have very big freedom degree, thus have very strong adaptability, are a kind of producing high-moleculars truly.
And this polymerization methods comply fully with the standard of Green Chemistry --- low energy consumption for normal-temperature reaction, organic solvent-free, without other tables
Face activating agent.
For other side, the present invention can make talan bisazo functional molecular be introduced into various height
In molecular material, it be dispersed in talan bisazo molecule can with molecular forms in macromolecule matrix, thoroughly solve it
The problem of being easy association aggregation, and the machinability of functional polymer is substantially improved, while talan can also be made double
The dosage of azo dyes greatly reduces, and has strictly prevented a possibility that functional material may pollute the environment.
Summary of the invention
Primary technical problem to be solved by this invention is to provide a kind of producing high-molecular side of talan bisazo dye
The characteristics of method, this method is first to synthesize a kind of amphipathic initiator containing talan bisazo functional group, then
The free radical generated at normal temperature using the redox reaction of initiator and potassium peroxydisulfate is caused water-soluble in water/oil phase interface
Property or oil-soluble monomer polymerization, eventually form the functional polymer containing talan bisazo groups.
Another technical problem to be solved by this invention is to provide the preparation method of above-mentioned functional initiator, it is conscientiously
It is feasible, it is easy to operate, it is easy to largely prepare.
It is poly- in olefinic monomer that another technical problem to be solved by this invention is to provide a kind of above-mentioned functional initiator
Conjunction prepares the concrete application in high molecular material.
1, the present invention solves technical solution used by primary technical problem are as follows: one kind contains talan bisazo function
The amphipathic initiator of group, chemical structure is as shown in Figure 1, it is a kind of functional surfactant, in potassium peroxydisulfate
Oxidation under, can repeatedly generate living radical, cause the polymerization of oiliness or aqueous olefinic monomer, to realize hexichol second
The purpose of alkene bisazo dye producing high-molecular.
It is beneficial that this method can be such that the two kinds of operations of functionalization and polymerization reaction do not interfere with each other, substantially increase
The adaptability and operation freedom degree of this method, can allow talan bisazo molecule to be introduced into many kinds by a kind of initiator
In the high molecular material of class；
It is beneficial that the tertiary amine structure in initiator can react at normal temperature with potassium peroxydisulfate, by constantly aoxidizing
Nitrogen-atoms repeatedly can generate living radical on α-carbon, can two-way initiation is aqueous or oiliness monomer polymerization, do not need to be added
Other solvents and emulsifier；
It is beneficial that talan bisazo unit can be adjusted in macromolecule material by the dosage of control monomer
Content in material thoroughly solves the problems, such as that talan bisazo molecule is easy association aggregation, while improving function high score
The processability of son, the talan bisazo dye of producing high-molecular can be used for coating, ink and as dye matrix pair
Polymer fiber material dyeing.
2, the present invention solves technical solution used by another technical problem are as follows: a kind of system of above-mentioned functional initiator
Preparation Method, synthetic route is as shown in figure 3, its characterization step are as follows: 1) 0.1mol talan bisazo phenol is dissolved in 400ml
In water, add 0.2mol NaOH, be gradually added into 0.2mol epoxychloropropane under stiring, control reacting liquid temperature 50~
55 DEG C of ranges, reaction time at 3~4 hours, add 0.22mol ethanol amine after the completion, and the reaction was continued at 30~35 DEG C 2~
3 hours, pH value then was acidified in 4.0~4.5 ranges with hydrochloric acid, a large amount of yellow mercury oxide occurs, deposit is collected and is used in combination
Clear water repeatedly washs, and is dried in vacuo after filtering；2) previous step obtained product is reacted to be dissolved in 300ml dehydrated alcohol,
The NaOH solid of 0.2mol iso-octyl glycidyl ether and 0.2mol is added under stiring, continues under 25~30 DEG C of range temperatures
Stirring 4~5 hours obtains golden yellow homogeneous reaction liquid, is concentrated with rotary evaporator to remove ethyl alcohol, finally obtains yellow
Solid matter, the product are exactly the functional initiator containing talan bisazo groups, it can disperse well in water.
3, the present invention solves technical solution used by another technical problem are as follows: above-mentioned functional initiator is anti-in polymerization
Application method in answering, characterization step are: 1) it disperses 18.0g functional initiator in 800mL water and is made into emulsion, it is dense
Degree control is in 2.0~2.5wt.% range；2) oil-soluble monomer vinylacetate is added in emulsion, monomer and initiator
Weight ratio in 1: 1~4: 1 range, potassium peroxydisulfate solid powder is added after being sufficiently stirred, dosage is investment initiator weight
2.0~3.0%, 5~after ten minutes polymerization reaction occur, system temperature is risen, and quickly forms the polymer of yellow
Particle, and color is hardly visible in water phase, polymerization reaction is completed in 1~2 hour, and collected particle is as hydrophobic
Talan bisazo dye producing high-molecular product；3) resulting polymers are dissolved in methyl alcohol after second step, it is dense
Degree is maintained at 10~15g/100ml range, adds the NaOH solid of polymer weight 5~7%, and reflux 2~3 is small under stiring
When, polymer is precipitated after reaction with yellow mercury oxide, and it is washed and is dried in vacuo with clear water after filtering, the yellow finally obtained
Solid matter contains polyvinyl alcohol segments, as hydrophilic talan bisazo dye producing high-molecular product.
It is beneficial that this polymerization rate is fast, high conversion rate, monomer can be gradually added into polymerization process,
Convenient for controlling reaction temperature；
It is beneficial that being added without other organic solvents in entire polymerization process, exacting terms is not needed, is accorded with completely
Close the requirement of Green Chemistry.
The present invention has the advantages that 1) functionalization is not interfere with each other with polymerization reaction, operation freedom degree is big；2) a kind of initiator
Diversified functional polymer can be manufactured, it is adaptable；3) polymeric reaction condition is mildly controllable, and low energy consumption does not have to
Other organic solvents and emulsifier, products pure meet the requirement of Green Chemistry.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
The preparation of functional initiator:
Using talan bisazo phenol as starting material, this raw material has been commercialized, so being prepared with for it is ready-made
Method, be not repeated herein, be specific preparation step below:
1) 0.1mol talan bisazo phenol is dissolved in 400ml water, adds 0.2mol NaOH, under stiring
It is gradually added into 0.2mol epoxychloropropane, controls reacting liquid temperature in 50~55 DEG C of ranges, the reaction time at 3~4 hours, completes
After add 0.22mol ethanol amine, the reaction was continued at 30~35 DEG C 2~3 hours, is then acidified to pH value 4.0 with hydrochloric acid
There is a large amount of yellow mercury oxide in~4.5 ranges, collect deposit and are repeatedly washed with clear water, are dried in vacuo after filtering；
2) previous step is reacted obtained product to be dissolved in 300ml dehydrated alcohol, it is different that 0.2mol is added under stiring
The NaOH solid of octyl glycidyl ether and 0.2mol, continues stirring 4~5 hours under 25~30 DEG C of range temperatures, obtains gold
The homogeneous reaction liquid of yellow is concentrated to remove ethyl alcohol with rotary evaporator, finally obtains the solid matter of yellow, which is exactly
Functional initiator containing talan bisazo groups, it can disperse well in water.
The application method of functional initiator:
Using vinylacetate as the representative of oil-soluble monomer, it have the characteristics that simultaneously it is hydrophilic with oleophylic, by by institute
The polymer of acquisition further hydrolyzes, and can obtain the water soluble polymer product using polyvinyl alcohol as segment, specific poly-
Reaction is closed to carry out by following operating procedure:
1) disperse 18.0g functional initiator in 800mL water and be made into emulsion, concentration control 2.0~
2.5wt.% range；
2) 18g, 36g, 54g and 72g monomer vinylacetate are added separately to carry out in the emulsion of different batches more
Secondary parallel test, after being sufficiently stirred be added potassium peroxydisulfate solid powder, dosage be investment functional initiator weight 2.0~
3.0%, 5~polymerization reaction generation after ten minutes, system temperature can rise to 40~45 DEG C or so from 15~20 DEG C, and shape quickly
The polymer beads of yellowly, polymerization reaction terminate in 1~2 hour, at this time in water phase almost without color, collected
Grain is hydrophobic talan bisazo dye producing high-molecular product；
3) resulting polymers are dissolved in methyl alcohol after second step, concentration is maintained at 10~15g/100ml model
It encloses, adds the NaOH solid of polymer weight 5~7%, flow back 2~3 hours under stiring, polymer is after reaction with Huang
Color Precipitation is washed and is dried in vacuo with clear water after filtering, and the solid matter of the yellow finally obtained contains polyvinyl alcohol chain
Section, as hydrophilic talan bisazo dye producing high-molecular product.
The analysis of components of producing high-molecular product:
Two kinds of structures are mainly contained in polymer, one is the segment after polymerizing olefin monomers, another kind is exactly to cause
The mass ratio of agent itself, the two can be analyzed by absorbance, and the initiator of 1g is dissolved in 100ml solvent, is measured
Its absorbance is A1, then 1g polymer samples are dissolved in the solvent of 100ml, and measuring its absorbance is A2, due to being the same
Extinction group, then its maximum absorption wavelength be also it is the same, acquired results will have relational expression M/I=A1/A2- 1, wherein M/I
It is the ratio between polymerized segment quality and initiator quality in sample, this value should be with monomer mass in polymerization reaction and initiator matter
For the ratio between amount there are dependence, the two values are more abundant closer to illustrating to polymerize.Experimental result is summarised in Fig. 4, generally speaking M/I
With m/I mapping substantially near diagonal line, illustrate that the conversion ratio of monomer is relatively high, producing high-molecular effect is more satisfactory.
Explanation about application method:
Functional initiator is maximum in use to be characterized in that its dosage will draw considerably beyond general initiator
The dosage for sending out agent is the 20~100% of monomer weight, this is because what the present invention studied is not initiator in general sense,
Its purpose is not only initiated polymerization, it is often more important that introduces functional group, assurance function component occupies in the material
Certain specific gravity, if specific gravity cannot be referred to as functional material very little.This specific gravity can according to specific applicable cases into
Row is adjusted.
Detailed description of the invention
The chemical structure of Fig. 1 functional initiator.
The principle of Fig. 2 Redox Initiator water-oil phase polymerization.
The synthetic route of Fig. 3 functional initiator.
The relationship of Fig. 4 polymer material composition and feed ratio.
Claims (1)
1. a kind of producing high-molecular method of talan bisazo dye, it is characterised in that caused using such as the functional of flowering structure
Agent:
The operating procedure of the producing high-molecular method is successively are as follows:
1) it disperses 18.0g functional initiator in 800mL water and forms emulsion, concentration is controlled in 2.0~2.5wt.% model
It encloses；
2) oil-soluble monomer vinylacetate is added in emulsion, the weight ratio of monomer and initiator is in 1: 1~4: 1 model
It encloses；Potassium peroxydisulfate solid powder is added after being sufficiently stirred, dosage is 2.0~3.0%, 5~10 points for putting into initiator weight
Clock post-polymerization occurs, and system temperature is risen, and quickly forms coloured polymer beads, and polymerization reaction is 1~2
It is completed in hour, and is hardly visible color in water phase, collected particle is hydrophobic talan bisazo dye
Producing high-molecular product；
3) resulting polymers being dissolved in methyl alcohol after second step, concentration is maintained at 10~15g/100ml range, then
The NaOH solid of polymer weight 5~7% is added, flows back 2~3 hours under stiring, polymer is heavy with yellow after reaction
Precipitation goes out, and is washed and is dried in vacuo with clear water after filtering, and the solid matter of the yellow finally obtained contains polyvinyl alcohol segments, i.e.,
For hydrophilic talan bisazo dye producing high-molecular product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810412053.2A CN109134723B (en) | 2018-04-18 | 2018-04-18 | Method for polymerizing stilbene disazo dye |
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| CN201810412053.2A CN109134723B (en) | 2018-04-18 | 2018-04-18 | Method for polymerizing stilbene disazo dye |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220010869A (en) * | 2020-07-20 | 2022-01-27 | 한국화학연구원 | Photofunctional azobenzene compound and uses thereof |
| KR20220010906A (en) * | 2020-07-20 | 2022-01-27 | 한국화학연구원 | Photo-active compound with short alkyl group and a method of preparing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic 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 |
| CN105884640A (en) * | 2015-06-12 | 2016-08-24 | 宁波大学 | Dianion interface initiator and preparation method thereof |
-
2018
- 2018-04-18 CN CN201810412053.2A patent/CN109134723B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884640A (en) * | 2015-06-12 | 2016-08-24 | 宁波大学 | Dianion interface initiator and preparation method thereof |
| CN105820275A (en) * | 2015-07-08 | 2016-08-03 | 宁波大学 | Gemini type cationic 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220010869A (en) * | 2020-07-20 | 2022-01-27 | 한국화학연구원 | Photofunctional azobenzene compound and uses thereof |
| KR20220010906A (en) * | 2020-07-20 | 2022-01-27 | 한국화학연구원 | Photo-active compound with short alkyl group and a method of preparing the same |
| KR102454194B1 (en) | 2020-07-20 | 2022-10-14 | 한국화학연구원 | Photo-active compound with short alkyl group and a method of preparing the same |
| KR102454184B1 (en) | 2020-07-20 | 2022-10-14 | 한국화학연구원 | Photofunctional azobenzene compound and uses thereof |
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