CN109134766A - A kind of producing high-molecular method of naphthalimide fluorescent dye - Google Patents

A kind of producing high-molecular method of naphthalimide fluorescent dye Download PDF

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Publication number
CN109134766A
CN109134766A CN201810411859.XA CN201810411859A CN109134766A CN 109134766 A CN109134766 A CN 109134766A CN 201810411859 A CN201810411859 A CN 201810411859A CN 109134766 A CN109134766 A CN 109134766A
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initiator
producing high
naphthalimide
polymerization
fluorescent dye
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CN109134766B (en
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李艳
张瑞丰
李赛赛
肖通虎
龙能兵
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Ningbo University
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Ningbo University
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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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F112/00—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 aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
    • 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
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/08—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkali metals

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  • 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)

Abstract

The present invention relates to a kind of producing high-molecular methods of naphthalimide fluorescent dye.It synthesizes one kind and contains 4- amino -1, the amphiphilic compound of 8- naphthalimide fluorophore 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, oil-soluble monomer styrene polymerization was both can trigger in water/oil interface, also it can trigger water-soluble monomer acrylamide polymerization, to realize the purpose of naphthalimide fluorescent 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

A kind of producing high-molecular method of naphthalimide fluorescent dye
Technical field
The present invention relates to functional polymer material synthesis technical field, especially a kind of high score of naphthalimide fluorescent dye Naphthalimide luminescent dye molecule can be introduced polyolefin macromolecular material by the new synthetic technology by sonization technology of preparing In 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.
1,8- naphthalimide and its derivative are the dyestuffs of a quasi-tradition, they are bright in colour, and degree of staining is good, weaving with Occupy an important seat in dyeing of plastics product.4- amino -1,8- naphthoyl imide compounds are a kind of important fluorescent dye (its generations Table product such as disperse yellow), there is strong yellow-green fluorescence, maximum absorption wavelength is in 410-430nm range, fluorescent emission wave It grows in 525-535nm range, mainly with the dyeing of the fibers such as acetate fiber, polyester, polyamide, can also be used for fluorescence spy in recent years Needle and fluorescence chemical sensor.Since its biggish conjugated structure necessarily brings rigidity, it is difficult to dissolve, it is difficult to disperse, it is difficult to add Work, dyefastness are poor.A kind of remodeling method is naphthalimide fluorescent molecule to be become to polymerizable monomer, but this transformation is being changed It is relatively difficult on, it is at high cost, it 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 Naphthalimide fluorophore, and itself have the characteristics that water, oil it is amphiphilic, can be located in water phase with oil phase interface, Free radical caused by this way can make monomer polymerization in water phase but also make the monomer polymerization in oily phase, the office of producing high-molecular Sex-limited to be broken, the type by changing monomer is obtained with various functional polymers, and the range of producing high-molecular is significantly Extension, thus it 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 standard-normal-temperature reaction of Green Chemistry, and low energy consumption, organic solvent-free, living without other surfaces Property agent.
For other side, the present invention can make naphthalimide fluorescent functional molecule be introduced into various high scores It in sub- material, be dispersed in naphthalimide fluorescent molecule can with molecular forms in macromolecule matrix, thoroughly solve it and be easy The problem of association aggregation, and the machinability of functional polymer is substantially improved, while the dosage of fluorescent material can also be made Greatly reduce, 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 method of naphthalimide fluorescent dye, The characteristics of this method is first to synthesize a kind of amphipathic initiator containing naphthalimide fluorescent functional group, then using drawing The free radical that the redox reaction of hair agent and potassium peroxydisulfate generates at normal temperature causes water-soluble or oil in water/oil phase interface Soluble monomers polymerization, eventually forms the functional polymer containing naphthalimide fluorophore.
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 naphthalimide fluorescent functional base The amphipathic initiator of group, chemical structure is as shown in Figure 1, it is a kind of functional surfactant, in potassium peroxydisulfate Under oxidation, living radical can be repeatedly generated, causes the polymerization of oiliness or aqueous olefinic monomer, to realize naphthalimide The purpose of fluorescent 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 naphthalimide fluorescent molecule to be introduced into numerous species by a kind of initiator High molecular material in；
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 naphthalimide unit and fluorescence unit can be adjusted in high molecular material by the dosage of control monomer In content, thoroughly solve the problems, such as that naphthalimide fluorescent molecule is easy association aggregation, while improving functional polymer Processability.
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) 4- naphthalene bromide imide fluorescent dye is dissolved in dioxy In six ring solvents, ethylenediamine is added, the molar ratio of fluorescent dye and butanediamine is 1: 2, the weight ratio of dyestuff and dioxane Control controls reacting liquid temperature in 80~100 DEG C of ranges in 1: 5~1: 6 ranges under stiring, the reaction time at 4~5 hours, It is cooled to room temperature, then is poured into clear water after the reaction was completed, collect deposit and repeatedly washed with clear water unreacted to remove Ethylenediamine and solvent are dried in vacuo after filtering, obtain fluorescent dye derivatives；2) previous step is reacted into obtained fluorescent dye Derivative is dispersed in the dehydrated alcohol of 8 times of weight, adds propane sultone, fluorescent dye derivatives and propane sultone Molar ratio control controls reaction temperature in 20~25 DEG C of ranges 1: 2 under stiring, be gradually added into after 1 hour in propane sulfonic acid The equimolar NaOH solid of ester, continues stirring 3~4 hours at room temperature, and fluorescent dye gradually dissolves in reaction process, final complete Fully dissolved forms homogeneous reaction solution, is then concentrated with rotary evaporator to remove ethyl alcohol, finally obtains the solids of yellow Matter, the product are exactly the functional initiator containing 4- amino -1,8- naphthalimide fluorophore, it can divide well in water It dissipates.
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) being dispersed in water 10.0g functional initiator to form emulsion, concentration control System is in 1.0~1.5wt.% range；2) oil-soluble monomer is added in emulsion, the weight ratio of monomer and initiator is 1: 1 ~4: 1 range, is added potassium peroxydisulfate solid powder after being sufficiently stirred, dosage is put into initiator weight 2.0~3.0%, 5 ~polymerization reaction generation after ten minutes, system temperature is risen, and quickly forms coloured polymer beads, and in water phase It is hardly visible color；If 3) monomer is water-soluble, monomer is same as the weight ratio of initiator in 1: 1~4: 1 range, that It will form aqueous solutions of polymers that is very sticky, having intense fluorescence after polymerization, can be polymerize after precipitating reagent is added Object solid.
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:
With 4- naphthalene bromide imide fluorescent dye starting material, ready-made side is prepared with about this raw material compound Method is not repeated herein, and is specific preparation step below:
1) 4- naphthalene bromide imide fluorescent dye is dissolved in dioxane solvent, adds ethylenediamine, fluorescent dye Molar ratio with butanediamine is 1: 2, and the weight ratio control of dyestuff and dioxane is in 1: 5~1: 6 ranges, and control is anti-under stiring Answer liquid temperature in 80~100 DEG C of ranges, the reaction time at 4~5 hours, is cooled to room temperature after the reaction was completed, then pours into clear water, It collects deposit and is repeatedly washed with clear water to remove unreacted ethylenediamine and solvent, be dried in vacuo, obtain glimmering after filtering Photoinitiator dye derivative；
2) previous step is reacted obtained fluorescent dye derivatives to be dispersed in the dehydrated alcohol of 8 times of weight, is added The molar ratio control of propane sultone, fluorescent dye derivatives and propane sultone controls reaction temperature under stiring and exists 1: 2 20~25 DEG C of ranges, be gradually added into after 1 hour with the equimolar NaOH solid of propane sultone, continue stirring 3~4 at room temperature Hour, fluorescent dye gradually dissolves in reaction process, is finally completely dissolved, forms homogeneous reaction solution, then use rotary evaporation Device is concentrated to remove ethyl alcohol, finally obtains the solid matter of yellow, which is exactly containing 4- amino -1,8- naphthalimide fluorescence The functional initiator of group, it can disperse well in water.
The application method of functional initiator:
Using styrene as the representative of oil-soluble monomer, using acrylamide as the representative of water-soluble monomer, polymerization reaction is pressed Following operating procedure carries out:
1) disperse 10.0g functional initiator in 800mL water, be made into emulsion, concentration control 1.0~ 1.5wt.% range；
2) 10g, 20g, 30g and 40g oil-soluble monomer styrene are added separately to carry out in the emulsion of different batches Multiple parallel test, is added potassium peroxydisulfate solid powder after being sufficiently stirred, and dosage is put into functional initiator weight 2.0 ~3.0%, 5~after ten minutes polymerization reaction occur, system temperature can rise to 40~45 DEG C or so from 20~25 DEG C, and quickly The polymer beads of yellow are formed, polymerization reaction terminates within half an hour, at this time in water phase almost without color, and styryl Originally it exhausts；
3) 10g, 20g, 30g and 40g water-soluble monomer acrylamide are added separately to different batches after the first step Multiple parallel test is carried out in secondary emulsion, adds potassium peroxydisulfate solid powder, and dosage remains as the initiation of investment function The 2.0~3.0% of agent weight, polymerization reaction 5~start after ten minutes, system temperature is risen, the reaction system of yellow Gradually become very sticky thick, half an hour post-polymerization terminates, and the solution methanol extraction finally obtained obtains the solid of yellow Substance illustrates fluorescent molecule all in the polymer almost without color in filtrate.
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, measuring its absorbance is A2, due to being the same Extinction group, then its maximum absorption wavelength is also equally, gained, which was tied, will relational expression M/I=A1/A2- 1, wherein M/I be The ratio between polymerized segment quality and initiator quality in sample, this value should be with monomer mass in polymerization reaction and initiator qualities The ratio between there are dependence, the two values are closer to illustrating that polymerization is more abundant.Experimental result is summarised in Fig. 4, generally speaking M/I with M/I maps substantially near diagonal line, illustrates 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 assessment of Fig. 4 producing high-molecular operating effect.

Claims (1)

1. a kind of producing high-molecular method of naphthalimide fluorescent 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) 10.0g functional initiator is dispersed in water to form emulsion, concentration is controlled in 1.0~1.5wt.% range；
2) oil-soluble monomer styrene is added in emulsion, the weight ratio of monomer and initiator is in 1: 1~4: 1 range；It fills Point stirring after be added potassium peroxydisulfate solid powder, dosage be investment initiator weight 2.0~3.0%, 5~gather after ten minutes Reaction is closed, system temperature is risen, and quickly forms coloured polymer beads, as hydrophobic naphthalimide Producing high-molecular product, and color is hardly visible in water phase；
3) be added water-soluble monomer acrylamide after the first step, the weight ratio of monomer and initiator 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 rises and increases sharply with viscosity, ultimately form it is very sticky, have it is strong yellowish green The aqueous solutions of polymers of color fluorescence can obtain polymer solids after precipitation agent methanol is added, as hydrophilic naphthalimide Producing high-molecular product.
CN201810411859.XA 2018-04-18 2018-04-18 High-molecular method of naphthalimide fluorescent dye Active CN109134766B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867737A (en) * 2019-02-27 2019-06-11 宁波大学 A kind of double type hydrazides anionic initiator and its preparation and application method

Citations (3)

* Cited by examiner, † Cited by third party
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
CN105884938A (en) * 2015-06-12 2016-08-24 宁波大学 Diphosphonate interface initiator and preparation method thereof
CN105884640A (en) * 2015-06-12 2016-08-24 宁波大学 Dianion interface initiator and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105884938A (en) * 2015-06-12 2016-08-24 宁波大学 Diphosphonate interface initiator and preparation method thereof
CN105884640A (en) * 2015-06-12 2016-08-24 宁波大学 Dianion interface 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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867737A (en) * 2019-02-27 2019-06-11 宁波大学 A kind of double type hydrazides anionic initiator and its preparation and application method
CN109867737B (en) * 2019-02-27 2022-03-18 宁波大学 Gemini type hydrazide anion initiator and preparation and use method thereof

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