CN105884640B - A kind of dianion interfacial initiation agent and preparation method thereof - Google Patents
A kind of dianion interfacial initiation agent and preparation method thereof Download PDFInfo
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Abstract
The present invention is on a kind of dianion interfacial initiation agent and preparation method thereof.Synthesize a kind of tertiary amine compound containing double carboxylate anions and double phenyl, it is set to show the feature of surfactant, with potassium peroxydisulfate redox reaction can occur for tertiary amine at normal temperatures simultaneously, radical cation is first formed on nitrogen-atoms, it is then converted into the carbon radicals of adjacent position, the generation of free radical can be repeated several times, flexibly control, realize multiphase concatenation polymerization, sequentially trigger the polymerization of styrene and butyl acrylate and styrene and DMAA in water/oil interface, obtain segmented copolymer, the rate of charge of experiment proof monomer and the ratio of components of copolymer are very consistent, illustrate that the efficiency of initiation of the initiator is higher, the polymeric reaction condition of this pattern is gently controllable, consume energy low, without other organic solvents and emulsifying agent, products pure, comply fully with the requirement of Green Chemistry.
Description
Technical field
The present invention relates to synthesis of polymer material technical field, especially a kind of dianion interfacial initiation agent and its chemistry
Preparation method, the new initiator can be used for the green syt of many kinds of polyolefin macromolecular materials.
Background technology
Polyolefin is a kind of very important high polymer material, and structure is adjustable, and species is various, is widely used.These materials
Typically olefinic monomer homopolymerization or copolymerization are obtained by initiator, different according to polymerization occasion, initiator can be divided into oil
Dissolubility and water-soluble two major classes, correspond to the polymerization of oil-soluble and water-soluble monomer, water soluble starter can also pass through respectively
Diffuse into the polymerization that emulsion microcapsules trigger oil-soluble monomer, the emulsion polymerization under being aided in here it is surfactant.Existing
In some polymerization techniques, initiator is a kind of compound that can produce free radical, and their use is by different monomers attribute
Restriction, design of the people to macromolecular structure often do one's utmost, and the improvement to initiator seems deficiency, although active
Radical polymerization technique can make the synthesis of block copolymer become simple and convenient, but these active free radical polymerizations typically can only
Carry out, can not accomplish across phase-polymerization in organic phase, synthesized block polymer feature deficiency, application value is limited, so far
The present can not large-scale popularization.The design of true high polymer material can also start with from the design of initiator, if certain initiator was both
Can polymerize the monomer in aqueous phase polymerize the monomer in oil phase with and can, breaks the obstacle that multi phase interface freely triggers, and realizes
The multiphase concatenation of polymerisation, then can plays obvious impetus to special high molecular synthesis.
Realize that the key of multiphase concatenation polymerization methodses is the strict positioning of initiator, only when initiator be in aqueous phase with
The interface of oil phase, it is possible to trigger the concatenation polymerization of water/oily two-phase, so initiator itself have to have surfactant
Characteristic.On the other hand, initiator, which must also assign it, flexibly can controllably produce the function of free radical, anti-using redox
Free radical should be produced 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 show redox reaction first occur on nitrogen-atoms, formed cation from
By base, hydrogen ion is then ionized out on adjacent carbon atom, forms carbon radicals, nitrogen-atoms can also oxygen again after being reduced
Change, until the hydrogen on adjacent carbon atom all disappears, this initiator a chain of can produce free radical and recycle (such as Fig. 2
It is shown).The polymerisation of oil phase can be triggered by being positioned at the free radical at interface, can also trigger the polymerisation of aqueous phase, due to this
The spike of two kinds of polymerizations comes from same initiator molecule, so what the hydrophobic chain and hydrophilic chain of generation were connected together,
Segmented copolymer is formed, here it is multiphase concatenation to polymerize, and its general principle is as shown in Figure 3.
Involved in the present invention is a case of this new polymerization methodses, and the initiator of design is a kind of dianion circle
Face initiator (as shown in Figure 1), it is in K2S2O8Under effect, free radical can be produced at normal temperatures, successfully trigger oiliness monomer benzene
The polymerization of ethene, butyl acrylate and hydrophilic monomer DMAA, obtain be difficult to obtain with other polymerization means two
The segmented copolymer of parent's property, and this polymerization methodses comply fully with the standard of Green Chemistry --- and normal-temperature reaction energy consumption is low, nothing
Organic solvent, without other surfactants.
The content of the invention
Primary technical problem to be solved by this invention is to provide a kind of dianion interfacial initiation agent, this initiator tool
There are water/oil interface locating features, and by the redox reaction with potassium peroxydisulfate, produce free radical at normal temperatures, energy is two-way
Trigger water-soluble and oil-soluble monomer, realize multiphase concatenation polymerization, can finally 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 is practical, easy to operate, is easy to largely prepare.
Another technical problem to be solved by this invention is to provide a kind of above-mentioned dianion interfacial initiation agent in benzene second
Concrete application in alkene/butyl acrylate/DMAA segmented copolymer preparation.
1st, technical scheme is used by the present invention solves primary technical problem：A kind of dual anion type interfacial initiation agent,
Its chemical constitution is as shown in figure 1, it is a kind of dianionic surfactant first, and under the oxidation of potassium peroxydisulfate,
Producing free radical can trigger monomer to polymerize, thus it is a kind of initiator again.
It is beneficial that this initiator can be positioned at the interface of water/oily two-phase, there is the energy of emulsive oily monomer
Power, thus no longer need to add other emulsifying agents, after initiated polymerization, it just turns into one of polymeric material
Point, emulsifying agent leakage problem will not be produced, will not also be had a negative impact to the performance of polymeric material；
It is beneficial that the tertiary amine in initiator can react at normal temperatures with potassium peroxydisulfate, interface free radical is produced, it is double
To the polymerization of water-based and oiliness monomer is triggered, segmented copolymer is synthesized by multiphase concatenation；
It is beneficial that this initiator repeatedly can produce free radical by constantly aoxidizing nitrogen-atoms on α-carbon,
So as to flexile control polymerisation, various of monomer is polymerize in a certain order, be advantageous to polyolefin
The MOLECULE DESIGN of family macromolecule material.
2nd, technical scheme is used by the present invention solves another technical problem：Draw at a kind of above-mentioned dual anion type interface
The preparation method of agent is sent out, its synthetic route is as shown in figure 4, its characterization step is：1) ethylenediamine is dissolved in absolute ethyl alcohol, second two
The weight of amine and ethanol is than controlling in 1: 3~1: 3.5 scopes, and being slowly added to methyl acrylate is stirred continuously, ethylenediamine and propylene
The mol ratio of sour methyl esters keeps 1: 2 as far as possible, and for control system temperature in 20~25 DEG C of scopes, it is small that the reaction time will reach 5~6
When；2) phenyl glycidyl ether is added into above-mentioned reactant mixture, the molal quantity of phenyl glycidyl ether should be with aforesaid propylene
The molal quantity of sour methyl esters is identical, reaction temperature is gradually raised to 40~50 DEG C under agitation, and reaction 4~5 is small at such a temperature
When；3) the 30wt.% NaOH aqueous solution is added into above-mentioned reaction solution, the molal quantity of sodium hydroxide should be methyl acrylate mole
Several 1.2~1.5 times, back flow reaction 4~5 hours at a temperature of 70~80 DEG C, reaction are poured the mixture into clear water after terminating,
Obtain the dispersion liquid of muddiness；4) above-mentioned dispersion liquid is acidified, pH value is less than 3, separate out white precipitate immediately, precipitation is filtered,
And washed with a small amount of clear water, then the NaOH aqueous solution precipitated with 10wt.% is handled, it is just dissolved, resulting solution is used
Rotary Evaporators concentrate, and obtain translucent solid matter interfacial initiation agent.
It is beneficial that in first step preparation, ethylenediamine is good with methyl acrylate reactivity, at a lower temperature
Its high conversion rate is reacted, is easily controlled, methyl acrylate residual is few, and next reaction is can be carried out without separating-purifying；
It is beneficial that in the preparation of the 4th step, product is easily washed out with inner salt form, can doing with filtration washing
Method separation product, ensure purity.
3rd, technical scheme is used by the present invention solves another technical problem：Above-mentioned dianion interfacial initiation agent exists
Application process in polyolefin synthesis, its characterization step are：1) dual anion type interfacial initiation agent is soluble in water, concentration is general
In 1.5~2.0 ‰ scopes, the dosage of initiator is usually the 2.0~2.5% of the first monomer weight；2) oil-soluble monomer is added
Enter into emulsion, addition potassium peroxydisulfate solid powder (generally the 1.0~1.5% of monomer weight) after being sufficiently stirred, about 5
Post-polymerization occurs within~10 minutes, and system temperature has risen, and quickly forms polymer emulsion；3) second of list is added
Body, if second comonomer is oil-soluble, then the Polymer absorption that it can have been formed, add second batch potassium peroxydisulfate
Afterwards, polymerisation restarts, and the diameter of emulsion particle becomes big, finally obtains the copolymer of more blocks；If second of monomer
It is water miscible, then after same operation, obtain amphipathic block copolymer.
It is beneficial that because free radical only produces at interface, oiliness monomer concentration is high, thus polymerisation is fast, turns
Rate is high, and monomer can be sequentially added into polymerization process, is very easy to the composition and structure of control polymer；
It is beneficial that it is added without other organic solvents in whole polymerization process, it is not necessary to exacting terms, completely symbol
Close the requirement of Green Chemistry.
The advantage of the invention is that：1) it can realize that multiphase concatenates aggregation scheme using new initiator, i.e., it is a kind of to trigger
Agent can complete the polymerization of various ways；2) composition and structure of polymer are easily controlled, can be implemented according to actual requirement more
The random collocation of kind block；3) polymeric reaction condition is gently controllable, and power consumption is low, without other organic solvents and emulsifying agent, product
It is pure, comply fully with the requirement of Green Chemistry.
Embodiment
The present invention is described in further detail with reference to embodiments.
The preparation of dianion interfacial initiation agent：
1st, ethylenediamine is dissolved in absolute ethyl alcohol, the weight of ethylenediamine and ethanol is delayed than controlling in 1: 3~1: 3.5 scopes
The slow methyl acrylate that adds is stirred continuously, and the mol ratio of ethylenediamine and methyl acrylate keeps 1: 2 as far as possible, control system temperature
In 20~25 DEG C of scopes, the reaction time will reach 5~6 hours；
2nd, add phenyl glycidyl ether into above-mentioned reactant mixture, the molal quantity of phenyl glycidyl ether should with it is above-mentioned
The molal quantity of methyl acrylate is identical, and reaction temperature is gradually raised to 40~50 DEG C under agitation, and at such a temperature reaction 4~
5 hours；
3rd, the 30wt.% NaOH aqueous solution is added into above-mentioned reaction solution, the molal quantity of sodium hydroxide should be acrylic acid first
1.2~1.5 times of ester molal quantity, back flow reaction 4~5 hours at a temperature of 70~80 DEG C, reaction pour the mixture into after terminating
In clear water, the dispersion liquid of muddiness is obtained；
4th, above-mentioned dispersion liquid is acidified, make pH value be less than 3, separate out white precipitate immediately, will precipitation filtering, and with a small quantity it is clear
Water washing, then the NaOH aqueous solution precipitated with 10wt.% is handled, it is just dissolved, by resulting solution Rotary Evaporators
Concentration, 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 is dissolved in 650mL water, is made into emulsion, concentration typically 1.5~
2.0 ‰ scopes；
B. 55g oil-soluble monomer styrene is added in emulsion, 0.6g potassium peroxydisulfate solids is added after being sufficiently stirred
Powder the 1.0~1.5% of monomer weight (generally), post-polymerization occurs within about 5~10 minutes, system temperature can from 20~
25 DEG C rise to 40~45 DEG C or so, and quickly form white polystyrene emulsion, and polymerisation typically terminates within half an hour,
Now styrene exhausts substantially；
C. different amounts of second of monomer butyl acrylate is added, monomer is absorbed by polystyrene emulsion quickly, Ran Houjia
Enter second batch potassium peroxydisulfate (weight of butyl acrylate 1%), polymerisation restarts, and system temperature is begun to ramp up again, breast
The diameter of liquid particles becomes big, finally obtains the copolymer containing polystyrene and butyl polyacrylate block；
D. the DMAA of different weight is added after the second the end of the step as second of monomer, after its dissolving
Potassium peroxydisulfate (the 1% of acrylamide weight) is added, restarting is reacted after of short duration induction period, the viscosity of system is bright
Aobvious increase, finally obtains the amphipathic copolymer with two kinds of blocks of styrene and DMAA, above-mentioned emulsion product
With all obtaining solid product after methanol extraction.
Product analysis：Weighed by comparing after polymerisation twice monomeric charge than the uniformity with copolymer ratio of components
The actual effect of the initiator, the reactant mixture methanol extraction of unit volume is removed that may be present after polymerization every time
The small-molecule substances such as monomer, weighed after the scrubbed drying of resulting polymer, just obtain polymer output, polymerize for the first time
To the yield of polystyrene, the yield of copolymer is obtained after polymerizeing for second, thus extrapolates two kinds of blocks in copolymer
Quality ratio of components M1/M2, and rate of charge m1/m2The mass ratio of the two kinds of monomers added in exactly testing.To each the second list
Body carries out four combined polymerizations experiment, and resulting the experimental results are shown inthe following table, it can be found that rate of charge has with ratio of components from table
There is good uniformity, illustrate each polymerisation all than more thoroughly, that is to say, that the efficiency of initiation of initiator is higher.
The rate of charge of polymerisation compares with the ratio of components of copolymer
Brief description of the drawings
The chemical constitution of Fig. 1 dual anion type interfacial initiation agent.
Fig. 2 Redox Initiator principles.
Fig. 3 multiphases concatenate polymerization methodses schematic diagram.
The synthetic route of Fig. 4 dual anion type interfacial initiation agent.
Claims (1)
1. a kind of preparation method of dianion interfacial initiation agent, the structure of the initiator are：
It is characterized in that step is followed successively by：
1) ethylenediamine is dissolved in absolute ethyl alcohol, the weight of ethylenediamine and ethanol slowly adds than controlling in 1: 3~1: 3.5 scopes
Enter methyl acrylate to be stirred continuously, the mol ratio of ethylenediamine and methyl acrylate keeps 1: 2 as far as possible, and control system temperature is 20
~25 DEG C of scopes, reaction time will reach 5~6 hours；
2) phenyl glycidyl ether is added into above-mentioned reactant mixture, the molal quantity of phenyl glycidyl ether should be with aforesaid propylene
The molal quantity of sour methyl esters is identical, reaction temperature is gradually raised to 40~50 DEG C under agitation, and reaction 4~5 is small at such a temperature
When；
3) the 30wt.% NaOH aqueous solution is added into above-mentioned reaction solution, the molal quantity of sodium hydroxide should be methyl acrylate and rub
1.2~1.5 times of that number, back flow reaction 4~5 hours at a temperature of 70~80 DEG C, reaction pours the mixture into clear water after terminating
In, obtain the dispersion liquid of muddiness；
4) above-mentioned dispersion liquid is acidified, pH value is less than 3, separate out white precipitate immediately, precipitation is filtered, and is washed with a small amount of clear water
Wash, then the NaOH aqueous solution precipitated with 10wt.% handled, it is just dissolved, resulting solution is concentrated with Rotary Evaporators,
Obtain translucent solid matter interfacial initiation agent.
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| CN109134723B (en) * | 2018-04-18 | 2021-05-18 | 宁波大学 | Method for polymerizing stilbene disazo dye |
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| CN109134735B (en) * | 2018-04-18 | 2021-04-30 | 宁波大学 | High-molecular method of disperse scarlet dye S-BWFL |
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| US11084974B2 (en) | 2018-08-29 | 2021-08-10 | Championx Usa Inc. | Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations |
| US11292734B2 (en) | 2018-08-29 | 2022-04-05 | Ecolab Usa Inc. | Use of multiple charged ionic compounds derived from poly amines for waste water clarification |
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| 油田用阴离子双子表面活性剂的合成与应用研究进展;胡小冬 等;《石油与天然气化工》;20111231;第40卷(第5期);第4、494-498页 * |
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