CN105820273A - Gemini cationic surface active initiator and preparation method thereof - Google Patents
Gemini cationic surface active initiator and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a gemini cationic surface active initiator and a preparation method thereof. The method is characterized in that an amphiphilic compound containing disulfonic acid and bis-isooctane is synthesized, so that the compound has strong characteristic of an emulsification oiliness monomer, simultaneously, hydrophilic tertiary amine and potassium persulphate are subjected to an oxidation reduction reaction at normal temperature, cation free radical is formed on the nitrogen atoms, then conversed to the carbon free radicals with adjacent position, the generation of the free radical enables multi-time repetition with flexible control, a continuously initiated polyphase series-connection polymerization mode is realized, polymerization of styrene and vinyl acetate as well as styrene and acrylamide can be initiated on a water/oil interface in order, a segmented copolymer is obtained, the experiment proves that monomer feeding ratio and copolymer components ratio are consistent, initiation efficiency of the initiator is high, the polymerization condition in this mode is mild and controllable, energy consumption is low, other organic solvents and emulsifiers are not required, and products are pure and completely accord with green chemistry requirement.
Description
Technical field
The present invention relates to synthesis of polymer material technical field, especially a kind of double type anion surface active initiator and chemical preparation process thereof, this new initiator can be used for many green syt planting TPO macromolecular material.
Background technology
Polyolefin is a very important universal macromolecular material of class, and structure can easily be accommodated, thus various in style, is widely used.These materials are typically all and make olefin monomer homopolymerization or copolymerization obtain by initiator, different according to polymerization occasion, initiator can be divided into 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 by diffusing in small emulsion micelles, can also cause the polymerization of oil-soluble monomer.In general initiator is the compound that a class can produce free radical, such as oil-soluble peroxide initiator, azo-initiator and water miscible persulfate.After initiator once decomposes, its collapsed portion becomes the end group of macromolecular chain, the most active.The living radical polymerization technique that development in recent years is got up can make the free radical of end again cause polymerization, thus make the synthesis of block copolymer become simple and convenient, but these active free radical polymerizations typically can only be carried out in organic facies, cannot accomplish across phase-polymerization, synthesized block polymer structures excursion is limited, actual application value seems not enough, so far cannot large-scale popularization.In the evolution of macromolecular material, the design of macromolecular structure is often done one's utmost by people, but the improvement to initiator seems not enough, and in fact the design of initiator is also a very important link, it brings beyond thought convenience can to the MOLECULE DESIGN of macromolecular material.It is fully able to give two important characteristics of initiator by MOLECULE DESIGN: one is to make the monomer polymerization in aqueous phase that the monomer in oil phase can be made again to be polymerized；Two is can repeatedly to produce free radical, is caused the heterogeneous concatenation realizing polyreaction by the chain of rings, thus is greatly increased the development space of TPO macromolecular material.
Realizing the strict location that it is critical only that initiator of heterogeneous concatenation polymerization methods, be only in the interface of aqueous phase and oil phase when initiator, it its is possible to the concatenation polymerization causing water/oil biphase, so initiator itself have to have the characteristic of surfactant.On the other hand, initiator must also controllably produce free radical, and best bet utilizes redox reaction exactly, and wherein reducing agent is the trimethylamine molecule of main body-amphipathic of initiator, and oxidant is the water solublity K of auxiliary2S2O8Redox reaction first occurs on nitrogen-atoms, form radical cation, then power at adjacent carbon atom and separate out hydrion, form carbon radicals, nitrogen-atoms can be with repeated oxidation after being reduced, until the hydrogen atom on adjacent carbon atom all ionizes, so this initiator repeatedly can produce free radical and recycle (as shown in Figure 2).Interface free radical can cause the polyreaction of oil phase, also can cause the polyreaction of aqueous phase, the spike of both polymerizations is from same initiator molecule, so what the hydrophobic chain generated and hydrophilic chain were connected together, here it is heterogeneous concatenation polymerization, its ultimate principle is as shown in Figure 3.
The present invention relates to a case of this new polymerization methods, designed initiator is a kind of double type anion surface active initiator, namely being combined by two surfactant molecules, it has the emulsification function more higher than conventional surfactants, uses K at normal temperatures2S2O8Energy of oxidation produces free radical, successfully cause styrene, vinylacetate and hydrophilic monomer acrylamide polymerization, obtain and be difficult to, by other polymerization means, the segmented copolymer that obtains, and this polymerization methods complies fully with that the standard one normal-temperature reaction energy consumption of Green Chemistry 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 double type anion surface active initiator, this initiator has water/oil interface locating features, and by the redox reaction with potassium peroxydisulfate, the free radical two-way initiation water solublity of energy produced at normal temperatures and oil-soluble monomer, realize heterogeneous concatenation polymerization, finally can form segmented copolymer.
Another technical problem to be solved by this invention is to provide the preparation method of above-mentioned double type anion surface active initiator, and it is practical, easy and simple to handle, it is easy to prepare in a large number.
Another technical problem to be solved by this invention is to provide the concrete application in styrene/vinylacetate/acrylamide segmented copolymer preparation of a kind of above-mentioned double type anion surface active initiator.
1, the present invention solves the technical scheme that primary technical problem used and is: a kind of double type anion surface active initiator, its chemical constitution is as shown in Figure 1, first it is a kind of double type anion surfactant, and under the Oxidation of potassium peroxydisulfate, free radical can be produced and cause the polymerization of water/oily biphase monomer, thus it is again a kind of initiator.
Very usefully, the initiator of this double type structure has the ability of the emulsive oily monomer more higher than conventional surfactants, 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, the two-way initiation aqueous of energy and the polymerization of oiliness monomer, it is achieved heterogeneous concatenation aggregation scheme, be easily created segmented copolymer；
Very usefully, this initiator can repeatedly produce free radical by continuous nitrogen oxide atom on alpha-carbon, polyreaction can be controlled versatile and flexiblely, various of monomer can be made to be polymerized according to the order fed intake, beneficially the MOLECULE DESIGN of TPO macromolecular material.
2, the present invention solves the technical scheme that another technical problem used and is: the preparation method of a kind of above-mentioned double type anion surface active initiator, its synthetic route is as shown in Figure 4, its characterization step is: 1) by octyl glycidyl ether and ethylenediamine as far as possible according to 2: 1 mixed in molar ratio and be dissolved in dehydrated alcohol, octyl glycidyl ether controls in 1: 2.5～1: 3 scope with the weight ratio of ethanol, under agitation control reaction temperature is 25～30 DEG C of scopes, and the response time was at 5～6 hours；2) in above-mentioned reactant liquor, propane sultone is added, propane sultone controls 1: 1 with the mol ratio of octyl glycidyl ether as far as possible, under agitation control reaction temperature 30～40 DEG C of scopes, solid LiOH is added after reacting 1～2 hour, the molal quantity of LiOH is identical with the molal quantity of propane sultone, stir 2～3 hours under room temperature, be completely dissolved to LiOH；3) concentrating removing ethanol by rotary evaporator, finally obtain semi-solid whiteness, this product is exactly double type anion surface active initiator, and it well can disperse in water.
It is beneficial that when octyl glycidyl ether is with reacting ethylenediamine, controls temperature and advantageously form Shuangzi structure, propane sultone reactivity is high, and it is just easily introduced azochlorosulfonate acid anion after reacting with secondary amine；
End product can be made to dissolve in ethanol it is beneficial that add LiOH, be conducive to being smoothed out of reaction, and ensure the purity of product.
3, the present invention solves the technical scheme that another technical problem used and is: above-mentioned double type anion surface active initiator application process in polyolefin synthesizes, its characterization step is: 1) by soluble in water for double type anion surface active initiator, concentration is typically in 1.0～1.5 ‰ scopes, and the consumption of initiator is usually the 1.0～1.5% of the first monomer weight；2) oil-soluble monomer is joined in emulsion, potassium peroxydisulfate pressed powder (generally putting into the 1.0～1.5% of monomer weight) is added after being sufficiently stirred for, within about 5～10 minutes, post-polymerization occurs, and system temperature has risen, and quickly forms polymer emulsion；3) adding the second monomer, if second comonomer is oil-soluble, then the Polymer absorption that it can have been formed, after adding second batch potassium peroxydisulfate, polyreaction restarts, and the diameter of emulsion particle becomes big, finally obtains the copolymer of many blocks；If the second monomer 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, and conversion ratio 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, comply fully with the requirement of Green Chemistry.
It is an advantage of the current invention that: 1) utilize new initiator can realize heterogeneous concatenation aggregation scheme, a kind of initiator can complete the polymerization of various ways；2) it is easily controlled composition and the structure of polymer, the random collocation of multiple block can be implemented according to actual requirement；3) polymeric reaction condition gentleness is controlled, low energy consumption, without other organic solvent and emulsifying agent, products pure, complies 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 double type anion surface active initiator:
1, octyl glycidyl ether and ethylenediamine are dissolved in dehydrated alcohol according to the mixed in molar ratio of 2: 1 as far as possible, octyl glycidyl ether controls in 1: 2.5～1: 3 scope with the weight ratio of ethanol, under agitation control reaction temperature is 25～30 DEG C of scopes, and the response time was at 5～6 hours；
2, in above-mentioned reactant liquor, propane sultone is added, propane sultone controls 1: 1 with the mol ratio of octyl glycidyl ether as far as possible, under agitation control reaction temperature 30～40 DEG C of scopes, solid LiOH is added after reacting 1～2 hour, the molal quantity of LiOH is identical with the molal quantity of propane sultone, stir 2～3 hours under room temperature, be completely dissolved to LiOH；
3, concentrating removing ethanol by rotary evaporator, finally obtain semi-solid whiteness, this product is exactly double type anion surface active initiator, and it well can disperse in water.
The use of initiator is carried out by following operating procedure:
A. being dissolved in 800mL water by 0.8g double type anion surface active initiator, be made into emulsion, concentration is typically in 1.0～1.5 ‰ scopes；
B. 70g oil-soluble monomer styrene is joined in emulsion, 0.8g potassium peroxydisulfate pressed powder (generally putting into the 1.0～1.5% of monomer weight) is added after being sufficiently stirred for, within about 5～10 minutes, post-polymerization occurs, system temperature can rise to about 40～45 DEG C from 20～25 DEG C, and quickly form white polystyrene emulsion, polyreaction typically terminated within half an hour, and now styrene exhausts substantially；
C. different amounts of the second monomer vinylacetate is added, quickly monomer is absorbed by polystyrene emulsion, it is subsequently adding second batch potassium peroxydisulfate (weight of vinylacetate 1%), polyreaction restarts, system temperature begins to ramp up again, the diameter of emulsion particle becomes big, finally obtains containing styrene and the copolymer of vinylacetate block；
D. after second step terminates, the acrylamide of Different Weight is added as the second monomer, potassium peroxydisulfate (the 1% of acrylamide weight) is added after it dissolves, react after of short duration induction period and restart, the viscosity of system significantly increases, finally obtain the amphipathic copolymer with polystyrene and polyacrylamide block, after above-mentioned emulsion product with methylalcohol precipitation, all obtain solid product.
Product analysis: weighed the actual effect of this initiator by monomeric charge after comparing twice polyreaction than the concordance with copolymer ratio of components, every time reactant mixture methanol extraction to unit volume after polymerization, the obtained scrubbed dried weighing of polymer, just obtain polymer output, polymerization for the first time obtains the yield of polystyrene, obtain the yield of copolymer after second time polymerization, thus extrapolate the quality ratio of components M of two kinds of blocks in copolymer1/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, it is found that rate of charge and ratio of components have good concordance from table, each polyreaction all ratios are described more thoroughly, say, that the efficiency of initiation of initiator 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 double type anion surface active initiator.
Fig. 2 redox initiation principle.
Fig. 3 heterogeneous concatenation polymerization methods schematic diagram.
The synthetic route of Fig. 4 double type anion surface active initiator.
Claims (5)
1. a double type anion surface active initiator, it is characterised in that this initiator has hydrophilic disulfonic acid root and hydrophobic double isobutyltrimethylmethane. bases, thus is easily present in water/oil interface, plays the effect of emulsifying agent.
Double type anion surface active initiator the most according to claim 1, it is characterized in that it contains two tertiary amine unit, it can occur redox reaction at normal temperatures with the potassium peroxydisulfate in aqueous phase, the nitrogen radical cation produced can change into alpha-carbon free radical, and this redox reaction can be repeated several times generation, different carbon atoms repeatedly produces free radical, thus can be repeatedly in water/oil interfacial initiation polyreaction.
Double type anion surface active initiator the most according to claim 1 and 2, it is characterized in that it can realize heterogeneous concatenation aggregation scheme, by different monomers is sequentially added into, just can obtain the copolymer of many blocks, polymerization process is easily controlled, synthesis condition is gentle, meets the requirement of Green Chemistry.
4. the preparation method of the double type anion surface active initiator described in a claim 1, it is characterised in that step is followed successively by:
1) octyl glycidyl ether and ethylenediamine are dissolved in dehydrated alcohol according to the mixed in molar ratio of 2: 1 as far as possible, octyl glycidyl ether controls in 1: 2.5～1: 3 scope with the weight ratio of ethanol, under agitation control reaction temperature is 25～30 DEG C of scopes, and the response time was at 5～6 hours；
2) in above-mentioned reactant liquor, propane sultone is added, propane sultone controls 1: 1 with the mol ratio of octyl glycidyl ether as far as possible, under agitation control reaction temperature 30～40 DEG C of scopes, solid LiOH is added after reacting 1～2 hour, the molal quantity of LiOH is identical with the molal quantity of propane sultone, stir 2～3 hours under room temperature, be completely dissolved to LiOH；
3) concentrating removing ethanol by rotary evaporator, finally obtain semi-solid whiteness, this product is exactly double type anion surface active initiator, and it well can disperse in water.
5. the using method of the double type anion surface active initiator described in a claim 1, it is characterized in that soluble in water for double type anion surface active initiator, concentration is typically in 1.0～1.5 ‰ scopes, the consumption of initiator is usually the 1.0～1.5% of the first monomer weight, and potassium peroxydisulfate consumption generally puts into the 1.0～1.5% of monomer weight.
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| CN106543388A (en) * | 2016-10-22 | 2017-03-29 | 宁波大学 | A kind of environment-friendly preparation method thereof of anionic PVDF membrane material |
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| CN113173869A (en) * | 2021-04-19 | 2021-07-27 | 三明学院 | Preparation method of fluorosulfonate-containing gemini surfactant |
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| CN109134769A (en) * | 2018-04-18 | 2019-01-04 | 宁波大学 | A kind of producing high-molecular method of imide fluorescent dye |
| CN109134766B (en) * | 2018-04-18 | 2021-05-18 | 宁波大学 | High-molecular method of naphthalimide fluorescent dye |
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| CN113173869A (en) * | 2021-04-19 | 2021-07-27 | 三明学院 | Preparation method of fluorosulfonate-containing gemini surfactant |
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Application publication date: 20160803 |