CN105884640A - Dianion interface initiator and preparation method thereof - Google Patents
Dianion interface initiator and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a dianion interface initiator and a preparation method thereof. A tertiary amine compound containing dicarboxylic acid radical anions and diphenyl groups is firstly synthesized to enable the tertiary amine compound to show the characteristics of a surfactant, tertiary amine can generate a redox reaction with potassium persulfate at room temperature, cation free radicals are firstly formed on nitrogen atoms and then converted into carbon free radicals at the adjacent positions, generation of the free radicals can be repeated for multiple times and flexibly controlled, multiphase concatenating polymerization is achieved, polymerization of styrene and butyl acrylate and polymerization of styrene and dimethyl acrylamide are initiated on a water-oil interface in sequence, and then a segmented copolymer is obtained. Experiments prove that the feed ratio of monomers is quite consistent with the component ratio of the copolymer, that is to say, the initiation efficiency of the initiator is very high, this mode of polymerization reaction is mild and controllable in condition and low in energy consumption, no other organic solvent or emulsifier is used, the product is pure, and the requirements of green chemistry are totally met.
Description
Technical field
The present invention relates to synthesis of polymer material technical field, especially a kind of dianion interfacial initiation agent and chemistry system thereof
Preparation Method, this new initiator can be used for many green syt planting TPO macromolecular material.
Background technology
Polyolefin is a very important macromolecular material of class, and structure is adjustable, of a great variety, is widely used.These materials
Material is typically all and olefinic monomer homopolymerization or copolymerization is obtained by initiator, and different according to polymerization occasion, initiator can divide
For oil-soluble and the big class of water solublity two, the most corresponding oil-soluble and the polymerization of water-soluble monomer, water soluble starter also may be used
To cause the polymerization of oil-soluble monomer by diffusing into emulsion microcapsule, here it is the emulsion under surfactant auxiliary is gathered
Close.In existing polymerization technique, initiator is a kind of compound that can produce free radical, and their use is not by
With the restriction of monomer attribute, the design of macromolecular structure is often done one's utmost by people, but the improvement to initiator seems
Not enough, although living radical polymerization technique can make the synthesis of block copolymer become simple and convenient, but these activity are certainly
It is polymerized by base and typically can only carry out in organic facies, it is impossible to accomplish that, across phase-polymerization, synthesized block polymer is functional not
Foot, using value is limited, so far cannot large-scale popularization.The design of true macromolecular material can also be from the design of initiator
Start with, if certain initiator can make the monomer polymerization in aqueous phase and the monomer in oil phase can be made to be polymerized again, break heterogeneous
The obstacle that interface is freely caused, it is achieved the heterogeneous concatenation of polyreaction, then just special high molecular synthesis can be played
Significantly impetus.
Realize the strict location that it is critical only that initiator of heterogeneous concatenation polymerization methods, be only in aqueous phase and oil when initiator
The interface of phase, it its is possible to the concatenation polymerization causing water/oil biphase, so initiator itself have to have surfactant
Characteristic.On the other hand, initiator must also give its function that can the most controllably produce free radical, utilizes oxidation also
Former reaction produces free radical at a lower temperature, and reducing agent therein is exactly the main body of initiator---amphipathic trimethylamine
Molecule, oxidant is water miscible K2S2O8, documents and materials display redox reaction first occurs on nitrogen-atoms,
Forming radical cation, then power at adjacent carbon atom and separate out hydrion, form carbon radicals, nitrogen-atoms is reduced
After can be with reoxidation, until the hydrogen on adjacent carbon atom all disappears, this initiator a chain of can produce free radical
And recycle (as shown in Figure 2).The free radical being positioned interface can cause the polyreaction of oil phase, also can cause
The polyreaction of aqueous phase, owing to the spike of both polymerizations is from same initiator molecule, so the hydrophobic chain generated
It is connected together with hydrophilic chain, forms segmented copolymer, here it is heterogeneous concatenation polymerization, its ultimate principle such as figure
Shown in 3.
Involved in the present invention is a case of this new polymerization methods, and the initiator of design is a kind of dianion interface
Initiator (as shown in Figure 1), it is at K2S2O8Under effect, free radical can be produced at normal temperatures, successfully cause oiliness
Monomer styrene, butyl acrylate and the polymerization of hydrophilic monomer DMAA, obtain being difficult to by other polymerization means
The amphipathic segmented copolymer obtained, and this polymerization methods complies fully with the standard of Green Chemistry---normal-temperature reaction
Energy consumption is low, organic solvent-free, without other surfactant.
Summary of the invention
Primary technical problem to be solved by this invention is to provide a kind of dianion interfacial initiation agent, and this initiator has
Water/oil interface locating features, and by the redox reaction with potassium peroxydisulfate, produce free radical at normal temperatures, can be double
To causing water solublity and oil-soluble monomer, it is achieved heterogeneous concatenation is polymerized, and finally can form segmented copolymer.
Another technical problem to be solved by this invention is to provide the preparation method of above-mentioned dianion interfacial initiation agent, it
Practical, easy and simple to handle, it is easy to prepare in a large number.
Another technical problem to be solved by this invention be to provide a kind of above-mentioned dianion interfacial initiation agent styrene/
Concrete application in butyl acrylate/DMAA segmented copolymer preparation.
1, the present invention solves the technical scheme that primary technical problem used and is: a kind of dual anion type interfacial initiation agent,
Its chemical constitution is as it is shown in figure 1, first it is a kind of dianionic surfactant, and at potassium peroxydisulfate
Under Oxidation, produce the polymerization of free radical energy trigger monomer, thus it is again a kind of initiator.
It is beneficial that this initiator can be positioned at the interface that water/oil is biphase, there is the ability of emulsive oily monomer,
Thus it is no longer necessary to add other emulsifying agent, once after initiated polymerization, it just becomes a part for polymeric material,
Emulsifying agent leakage problem will not be produced, also the performance of polymeric material will not be had a negative impact；
It is beneficial that the tertiary amine in initiator can react at normal temperatures with potassium peroxydisulfate, produce interface free radical, double
To causing aqueous and the polymerization of oiliness monomer, synthesize segmented copolymer by heterogeneous concatenation；
It is beneficial that this initiator repeatedly can produce free radical by continuous nitrogen oxide atom on alpha-carbon, from
And can flexile control polyreaction, make various of monomer be polymerized in a certain order, beneficially polyolefin
The MOLECULE DESIGN of family macromolecule material.
2, the present invention solves the technical scheme that another technical problem used and is: a kind of above-mentioned dual anion type interface is drawn
Sending out the preparation method of agent, as shown in Figure 4, its characterization step is its synthetic route: 1) ethylenediamine is dissolved in nothing
In water-ethanol, ethylenediamine controls, in 1: 3～1: 3.5 scope, to be slowly added to acrylic acid first with the weight ratio of ethanol
Ester is stirred continuously, and ethylenediamine keeps 1: 2 as far as possible with the mol ratio of acrylic acid methyl ester., controls system temperature and exists
20～25 DEG C of scopes, the response time to reach 5～6 hours；2) in above-mentioned reactant mixture, phenyl is added
Glycidyl ether, the molal quantity of phenyl glycidyl ether should be identical with the molal quantity of aforesaid propylene acid methyl ester,
Under stirring, reaction temperature is gradually raised to 40～50 DEG C, and reaction 4～5 hours at such a temperature；3) to above-mentioned
Adding the NaOH aqueous solution of 30wt.% in reactant liquor, the molal quantity of sodium hydroxide should be acrylic acid methyl ester. and rubs
1.2～1.5 times of your number, back flow reaction 4～5 hours at a temperature of 70～80 DEG C, reaction will mixing after terminating
Thing is poured in clear water, obtains the dispersion liquid of muddiness；4) above-mentioned dispersion liquid is acidified, makes pH value be less than 3,
Separate out white precipitate immediately, precipitation is filtered, and wash with a small amount of clear water, then by precipitation 10wt.%
NaOH aqueous solution processes so that it is just dissolve, and is concentrated by gained solution Rotary Evaporators, obtains semi-transparent
Bright solid matter interfacial initiation agent.
It is beneficial that in prepared by the first step, ethylenediamine is good with acrylic acid methyl ester. reactivity, at lower temperature
Its conversion ratio of lower reaction is high, is easily controlled, and acrylic acid methyl ester. residual is few, it is not necessary to it is anti-that separating-purifying can be carried out next portion
Should；
It is beneficial that in the 4th step preparation, product easily washes out with inner salt form, can be with filtration washing
Way separation product, it is ensured that purity.
3, the present invention solves the technical scheme that another technical problem used and is: above-mentioned dianion interfacial initiation agent exists
Application process in polyolefin synthesis, its characterization step is: 1) dual anion type interfacial initiation agent is dissolved in water
In, concentration is typically in 1.5～2.0 ‰ scopes, and the consumption of initiator is usually the first monomer weight
2.0～2.5%；2) oil-soluble monomer is joined in emulsion, after being sufficiently stirred for, add potassium peroxydisulfate solid
Powder (generally the 1.0～1.5% of monomer weight), within about 5～10 minutes, post-polymerization occurs, system temperature
Degree has risen, and quickly forms polymer emulsion；3) the second monomer is added, if second comonomer is oil
Dissolubility, then the Polymer absorption that it can have been formed, after adding second batch potassium peroxydisulfate, polymerization is anti-
Should restart, the diameter of emulsion particle becomes big, finally obtains the copolymer of many blocks；If the second list
Body is water miscible, then after same operation, it is thus achieved that amphipathic block copolymer.
It is beneficial that owing to free radical only produces at interface, oiliness monomer concentration is high, thus polyreaction is fast, turns
Rate is high, and in polymerization process, monomer can be sequentially added into, and is very easy to control composition and the structure of polymer；
It is beneficial that whole polymerization process is added without other organic solvent, it is not necessary to exacting terms, accord with completely
Close the requirement of Green Chemistry.
It is an advantage of the current invention that: 1) utilize new initiator can realize heterogeneous concatenation aggregation scheme, i.e. a kind of initiation
Agent can complete the polymerization of various ways；2) composition and the structure of polymer it are easily controlled, can be realistic according to being actually subjected to
Execute the random collocation of multiple block；3) polymeric reaction condition gentleness is controlled, consumes energy low, without other organic solvent and breast
Agent, products pure, comply fully with the requirement of Green Chemistry.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
The preparation of dianion interfacial initiation agent:
1, being dissolved in dehydrated alcohol by ethylenediamine, ethylenediamine controls in 1: 3～1: 3.5 scope, slowly with the weight ratio of ethanol
Adding acrylic acid methyl ester. to be stirred continuously, ethylenediamine keeps 1: 2 as far as possible with the mol ratio of acrylic acid methyl ester., controls
System temperature to reach 5～6 hours in 20～25 DEG C of scopes, response time；
2, adding phenyl glycidyl ether in above-mentioned reactant mixture, the molal quantity of phenyl glycidyl ether should be with above-mentioned
The molal quantity of acrylic acid methyl ester. is identical, under agitation reaction temperature is gradually raised to 40～50 DEG C, and in this temperature
The lower reaction of degree 4～5 hours；
3, adding the NaOH aqueous solution of 30wt.% in above-mentioned reactant liquor, the molal quantity of sodium hydroxide should be acrylic acid
1.2～1.5 times of methyl ester molal quantity, back flow reaction 4～5 hours at a temperature of 70～80 DEG C, reaction will after terminating
Mixture is poured in clear water, obtains the dispersion liquid of muddiness；
4, above-mentioned dispersion liquid is acidified, makes pH value be less than 3, separate out white precipitate immediately, precipitation is filtered, and with few
Amount clear water washing, then the NaOH aqueous solution of precipitation 10wt.% is processed so that it is just dissolve, by gained
Solution Rotary Evaporators concentrates, and obtains translucent solid matter interfacial initiation agent.
The use of initiator is carried out by following operating procedure:
A. 1.2g dual anion type interfacial initiation agent being dissolved in 650mL water, be made into emulsion, concentration typically exists
1.5～2.0 ‰ scopes；
B. 55g oil-soluble monomer styrene is joined in emulsion, add 0.6g potassium peroxydisulfate after being sufficiently stirred for solid
Body powder (generally the 1.0～1.5% of monomer weight), within about 5～10 minutes, post-polymerization occurs, body
It is that temperature can rise to about 40～45 DEG C from 20～25 DEG C, and quickly forms white polystyrene emulsion,
Polyreaction typically terminated within half an hour, and now styrene exhausts substantially；
C. adding different amounts of the second monomer butyl acrylate, quickly monomer is absorbed by polystyrene emulsion, then
Adding second batch potassium peroxydisulfate (weight of butyl acrylate 1%), polyreaction restarts, system temperature
Beginning to ramp up again, the diameter of emulsion particle becomes big, finally obtains containing polystyrene and butyl polyacrylate
The copolymer of block；
D. after second step terminates, add the DMAA of Different Weight as the second monomer, treat that it dissolves
After add potassium peroxydisulfate (the 1% of acrylamide weight), react after of short duration induction period and restart,
The viscosity of system significantly increases, and finally obtains and has styrene and the two of two kinds of blocks of DMAA
Parent's property copolymer, all obtains solid product after above-mentioned emulsion product with methylalcohol precipitation.
Product analysis: weigh this than the concordance with copolymer ratio of components by monomeric charge after comparing twice polyreaction
The actual effect of initiator, every time reactant mixture methanol extraction to unit volume after polymerization, removes that may be present
The small-molecule substances such as monomer, the scrubbed dried weighing of obtained polymer, just obtain polymer output, the most poly-
Close the yield obtaining polystyrene, obtain the yield of copolymer after second time polymerization, thus extrapolate two kinds in copolymer
The quality ratio of components M of block1/M2, and rate of charge m1/m2It it is exactly the mass ratio of the two kinds of monomers added in experiment.
Each second comonomer is carried out four combined polymerizations experiment, obtained experimental result is as shown in the table, from table it is found that
Rate of charge and ratio of components have good concordance, each polyreaction all ratios are described more thoroughly, say, that initiator
Efficiency of initiation is higher.
The rate of charge of polyreaction compares with the ratio of components of copolymer
Accompanying drawing explanation
The chemical constitution of Fig. 1 dual anion type interfacial initiation agent.
Fig. 2 redox initiation principle.
Fig. 3 heterogeneous concatenation polymerization methods schematic diagram.
The synthetic route of Fig. 4 dual anion type interfacial initiation agent.
Claims (5)
1. a dianion interfacial initiation agent, it is characterised in that this initiator have hydrophilic double carboxylate anions and
Hydrophobic double phenyl, thus easily it is present in water/oil interface, play the effect of emulsifying agent.
Dianion interfacial initiation agent the most according to claim 1, it is characterised in that it contains two tertiary amine unit,
They can occur redox reaction at normal temperatures with the potassium peroxydisulfate in aqueous phase, and the nitrogen cation of generation is freely
Base can change into alpha-carbon free radical, and this redox reaction can be repeated several times generation, at different carbon
Free radical is repeatedly produced on atom, thus can be at water/oil interface chain of rings initiated polymerization.
Dianion interfacial initiation agent the most according to claim 1 and 2, it is characterised in that it can realize heterogeneous string
Connect aggregation scheme, by being sequentially added into by different monomers, just can obtain the copolymer of many blocks, polymerization
Process is easily controlled, and synthesis condition is gentle, meets the requirement of Green Chemistry.
4. the preparation method of the dianion interfacial initiation agent described in a claim 1, it is characterised in that step is successively
For:
1) being dissolved in dehydrated alcohol by ethylenediamine, ethylenediamine controls in 1: 3～1: 3.5 scope with the weight ratio of ethanol,
Being slowly added to acrylic acid methyl ester. be stirred continuously, ethylenediamine keeps as far as possible with the mol ratio of acrylic acid methyl ester.
1: 2, control system temperature and to reach 5～6 hours in 20～25 DEG C of scopes, response time；
2) adding phenyl glycidyl ether in above-mentioned reactant mixture, the molal quantity of phenyl glycidyl ether should be with
The molal quantity of aforesaid propylene acid methyl ester is identical, under agitation reaction temperature is gradually raised to 40～50 DEG C,
And react 4～5 hours at such a temperature；
3) adding the NaOH aqueous solution of 30wt.% in above-mentioned reactant liquor, the molal quantity of sodium hydroxide should be third
1.2～1.5 times of e pioic acid methyl ester molal quantity, back flow reaction 4～5 hours at a temperature of 70～80 DEG C, reaction
Pour the mixture into after end in clear water, obtain the dispersion liquid of muddiness；
4) above-mentioned dispersion liquid is acidified, makes pH value be less than 3, separate out white precipitate immediately, precipitation is filtered, and
Wash with a small amount of clear water, then the NaOH aqueous solution of precipitation 10wt.% processed so that it is just dissolve,
Gained solution Rotary Evaporators is concentrated, obtains translucent solid matter interfacial initiation agent.
5. the using method of the dianion interfacial initiation agent described in a claim 1, it is characterised in that by jack to jack adapter from
Sub-interfacial initiation agent is soluble in water, and concentration is typically in 1.5～2.0 ‰ scopes, and the consumption of initiator is usually
The 2.0～2.5% of one monomer weight, potassium peroxydisulfate consumption generally puts into the 1.0～1.5% of monomer weight.
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| CN109134735A (en) * | 2018-04-18 | 2019-01-04 | 宁波大学 | A kind of producing high-molecular method of disperse scarlet dye S-BWFL |
| CN109134766A (en) * | 2018-04-18 | 2019-01-04 | 宁波大学 | A kind of producing high-molecular method of naphthalimide fluorescent dye |
| CN109134723A (en) * | 2018-04-18 | 2019-01-04 | 宁波大学 | A kind of producing high-molecular method of talan bisazo dye |
| JP2021535242A (en) * | 2018-08-29 | 2021-12-16 | エコラボ ユーエスエー インコーポレイティド | Multiple charged ionic compounds derived from polyamines and their compositions, and methods for preparing them. |
| US11565958B2 (en) | 2017-08-30 | 2023-01-31 | Ecolab Usa Inc. | Use of di-ionic compounds as corrosion inhibitors in a water system |
| US11639553B2 (en) | 2019-04-16 | 2023-05-02 | Ecolab Usa Inc. | Compositions comprising multiple charged cationic compounds derived from polyamines for corrosion inhibition in a water system |
| US11685709B2 (en) | 2018-08-29 | 2023-06-27 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations |
| US11702586B2 (en) | 2018-08-29 | 2023-07-18 | Championx Usa Inc. | Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations |
| US11926543B2 (en) | 2018-08-29 | 2024-03-12 | Ecolab Usa Inc. | Use of multiple charged ionic compounds derived from polyamines for waste water clarification |
| US12082580B2 (en) | 2018-08-29 | 2024-09-10 | Ecolab Usa Inc. | Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system |
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| CN109134766A (en) * | 2018-04-18 | 2019-01-04 | 宁波大学 | A kind of producing high-molecular method of naphthalimide fluorescent dye |
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| JP7171895B2 (en) | 2018-08-29 | 2022-11-15 | エコラボ ユーエスエー インコーポレイティド | Multiply-charged ionic compounds derived from polyamines and compositions thereof, and methods for their preparation |
| US11685709B2 (en) | 2018-08-29 | 2023-06-27 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations |
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