CN105884624B - A kind of polyhydroxy polyamines surface active initiator and preparation method thereof - Google Patents
A kind of polyhydroxy polyamines surface active initiator and preparation method thereof Download PDFInfo
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- CN105884624B CN105884624B CN201510340555.5A CN201510340555A CN105884624B CN 105884624 B CN105884624 B CN 105884624B CN 201510340555 A CN201510340555 A CN 201510340555A CN 105884624 B CN105884624 B CN 105884624B
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Abstract
The present invention is on a kind of polyhydroxy polyamines surface active initiator and preparation method thereof.Synthesize a kind of three tertiary amine compounds containing polyhydroxy and cetyl, 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 styrene and methyl acrylate and styrene and acrylamide polymerization in water/oil interface, obtain corresponding 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, energy consumption is 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 polyhydroxy polyamines surface active initiator and
Its chemical preparation process, the new initiator can be used for the green syt of olefines segmented copolymer.
Background technology
Polyolefin is a kind of very important high polymer material, and species is various, is widely used.These materials are typically all logical
Cross initiator to obtain olefinic monomer homopolymerization or copolymerization, different according to polymerization occasion, initiator can be divided into oil-soluble and water-soluble
Two major classes of property, are respectively used to the polymerization of oil-soluble and water-soluble monomer, water soluble starter can also be by diffusing into a subtle way
Small emulsion micelles trigger the polymerization of oil-soluble monomer.In existing high molecular polymerization technology, the cooperation of initiator and monomer
Not enough flexibly, it is necessary to which other supplementary means, a kind of few initiators, the monomer in aqueous phase can be made, which to polymerize and can, makes oil phase
In monomer polymerization.If assigning initiator more strong function, make the collocation of initiator and monomer not by aqueous phase and oil phase
The constraint at interface, realize the multiphase concatenation of polymerisation, then be just very beneficial for special high molecular synthesis.In macromolecule material
In the evolution of material, design of the people to macromolecular structure is often done one's utmost, but the improvement to initiator seems insufficient,
In fact the design of initiator is also a very important link, and it can bring to the MOLECULE DESIGN of high polymer material expects not
The convenience arrived.For example, living radical polymerization technique can make the synthesis of block copolymer become simple and convenient, but these are lived
The polymerization of free love base can only typically be carried out in organic phase, can not be accomplished across phase-polymerization, synthesized block polymer adaptability
Not enough, application value is limited, so far can not large-scale popularization.
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 must be able to produce free radical, and in order to realize the controllable generation of free radical, best bet is just
It is to produce free radical using redox reaction, reducing agent therein is organic uncle of the main body-amphipathic as initiator
Amine molecule, oxidant are water miscible K2S2O8, redox reaction first occurred on nitrogen-atoms, forms radical cation,
Then hydrogen ion is ionized out on adjacent carbon atom by Intramolecular electron transfer, forms carbon radicals, nitrogen-atoms returns to original
The state come, as long as can be with repeated oxidation, until all disappearances of the hydrogen on adjacent carbon atom, so this with the presence of oxidant
Initiator can produce free radical (as shown in Figure 2) with connecting ring type.Interface free radical can trigger the polymerisation of oil phase, can also draw
The polymerisation for phase of flooding, the spike of both polymerisations come from same initiator molecule, so the hydrophobic chain of generation
It is connected together with hydrophilic chain, 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 novel polymerizable mode, and the initiator of design is that a kind of polyhydroxy is more
Amine surface active initiator, it is in K2S2O8Under effect, free radical can be produced at normal temperatures, in no additional surfactants
In the presence of successfully trigger the polymerization of hydrophobic styrene, methyl acrylate and hydrophilic monomer acrylamide, obtain other polymerizations
Means are difficult to the amphipathic segmented copolymer obtained, and this polymerization methodses comply fully with the standard of Green Chemistry ---
Normal-temperature reaction energy consumption is low, organic solvent-free, without other surfactants.
The content of the invention
Primary technical problem to be solved by this invention is to provide a kind of polyhydroxy polyamines surface active initiator, this to draw
Hair agent has water/oil interface locating features, and by the redox reaction with potassium peroxydisulfate, at normal temperatures caused free radical
The two-way initiation water solubility of energy and oil-soluble monomer, realize multiphase concatenation polymerization, can form segmented copolymer.
Another technical problem to be solved by this invention is to provide the system of above-mentioned polyhydroxy polyamines surface active initiator
Preparation Method, 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 polyhydroxy polyamines surface active initiator
Concrete application in prepared by styrene/acrylic methyl esters/acrylamide segmented copolymer.
1st, technical scheme is used by the present invention solves primary technical problem：A kind of polyhydroxy polyamines surface living initiator
Agent, its chemical constitution is as shown in figure 1, it is a kind of surfactant first, caused and under the oxidation of potassium peroxydisulfate
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 polymerization is triggered, it just turns into a part for polymeric material, no
Emulsifying agent leakage problem can be produced, will not 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,
The characteristics of its chain of rings triggers is shown, polymerisation can be flexibly controlled, various of monomer is polymerize in a certain order, very
Be advantageous to the MOLECULE DESIGN of polyolefin macromolecular material.
Technical scheme is used by the present invention solves another technical problem：A kind of above-mentioned polyhydroxy polyamines surface-active
The preparation method of agent, its synthetic route is as shown in figure 4, its characterization step is：1) cetylamine is dissolved in absolute ethyl alcohol, cetylamine
Controlled with the weight ratio of ethanol in 1: 3~1: 3.5 scopes, add epoxychloropropane and be stirred continuously, cetylamine and epoxy chlorine
The mol ratio of propane keeps 1: 2 as far as possible, and for control system temperature in 25~30 DEG C of scopes, it is small that the reaction time will reach 15~16
When；2) diethanol amine and sodium hydroxide are added into above-mentioned reactant mixture, the molal quantity of diethanol amine and sodium hydroxide should be with
The molal quantity of above-mentioned epoxychloropropane is identical, and reaction temperature is gradually raised to 60~70 DEG C under agitation, now there is white precipitate
Separate out, this is NaCl fine crystals caused by reaction, is reacted 3~4 hours at such a temperature, gradually by NaCl crystal mistakes after cooling
Filter, and washed with a small amount of absolute ethyl alcohol, filtrate is concentrated with Rotary Evaporators, obtains sticky liquid, is become after being cooled to room temperature
Into semisolid, here it is polyhydroxy polyamines surface active initiator.
It is easily controlled, will not gathers it is beneficial that cetylamine reacts at a lower temperature with epoxychloropropane
Reaction is closed, the extent of reaction is high, and epoxychloropropane residual quantity is low；
It is beneficial that in second step preparation, diethanol amine reactivity is good, and yield is high, substituted chlorine atom
It is removed in the form of NaCl salt, is advantageous to the purifying of product.
2nd, technical scheme is used by the present invention solves another technical problem：Above-mentioned polyhydroxy polyamines surface-active is drawn
Application process of the agent in polyolefin synthesis is sent out, its characterization step is：1) polyhydroxy polyamines surface active initiator is dissolved in water
In, for concentration typically in 2.5~3.0 ‰ scopes, the dosage of initiator is usually the 2.5~3.0% of the first monomer weight；2) by oil
Soluble monomers are added in emulsion, and potassium peroxydisulfate solid powder is added after being sufficiently stirred and (generally puts into the 1.0 of monomer weight
~1.5%), about 5~10 minutes post-polymerizations occur, and system temperature has risen, and quickly forms polymer emulsion；3)
Second of monomer is added, if second comonomer is oil-soluble, then the Polymer absorption that it can have been formed, add second
After criticizing potassium peroxydisulfate, polymerisation restarts, and the diameter of emulsion particle becomes big, finally obtains the copolymer of more blocks；If
Second of monomer is water miscible, then after same operation, obtains 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, low energy consumption, 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 polyhydroxy polyamines surface active initiator：
1st, cetylamine being dissolved in absolute ethyl alcohol, the weight ratio of cetylamine and ethanol is controlled in 1: 3~1: 3.5 scopes, then
Add epoxychloropropane and be stirred continuously, the mol ratio of cetylamine and epoxychloropropane keeps 1: 2 as far as possible, control system temperature
In 25~30 DEG C of scopes, the reaction time will reach 15~16 hours；
2nd, the molal quantity of diethanol amine and sodium hydroxide, diethanol amine and sodium hydroxide is added into above-mentioned reactant mixture
Should be identical with the molal quantity of above-mentioned epoxychloropropane, reaction temperature is gradually raised to 60~70 DEG C under agitation, now there is white
Precipitation, this is NaCl fine crystals caused by reaction, is reacted 3~4 hours at such a temperature, gradually after cooling that NaCl is brilliant
Body is filtered, and is washed with a small amount of absolute ethyl alcohol, and filtrate is concentrated with Rotary Evaporators, sticky liquid is obtained, is cooled to room temperature
After become semi-solid, here it is polyhydroxy polyamines surface active initiator.
The use of initiator is carried out by following operating procedure：
A. 1.5g polyhydroxy polyamines surface active initiators are dissolved in 500mL water, are made into emulsion, concentration typically exists
2.5~3.0 ‰ 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 methyl acrylate is added, monomer is absorbed by polystyrene emulsion quickly, Ran Houjia
Enter second batch potassium peroxydisulfate (weight of methyl 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 PMA block；
D. the acrylamide of different weight is added after the second the end of the step as second of monomer, is added after its dissolving
Potassium peroxydisulfate (the 1% of acrylamide weight), reacts restarting after of short duration induction period, and the viscosity of system substantially increases
Greatly, the amphipathic copolymer with polystyrene and polyacrylamide block, above-mentioned emulsion product methanol extraction are finally obtained
Solid product is all obtained afterwards.
Product analysis：Weighed by comparing after polymerisation twice monomeric charge than the uniformity with copolymer ratio of components
The actual effect of the initiator, every time the reactant mixture methanol extraction of unit volume, removing are possible to deposit after polymerization
Small molecule monomer, weighed after the scrubbed drying of resulting polymer, just obtain polymer output, polymerization for the first time obtains
The yield of polystyrene, the yield of copolymer is obtained after second of polymerization, thus extrapolates the matter of two kinds of blocks in copolymer
Measure 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 second comonomer
Four combined polymerizations experiment is carried out, resulting the experimental results are shown inthe following table, it can be found that rate of charge has with ratio of components from table
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 polyhydroxy polyamines surface active initiators.
Fig. 2 Redox Initiator principles.
Fig. 3 multiphases concatenate polymerization methodses schematic diagram.
The synthetic route of Fig. 4 polyhydroxy polyamines surface active initiators.
Claims (1)
1. a kind of application method of polyhydroxy polyamines surface active initiator, it is characterised in that the structural formula of the initiator is：
Described application method is characterised by operating according to the following steps：
1) 1.5g polyhydroxy polyamines surface active initiators are dissolved in 500mL water, are made into emulsion, concentration control 2.5~
3.0 ‰ scopes；
2) 55g oil-soluble monomer styrene is added in emulsion, 0.6g potassium peroxydisulfate solid powders is added after being sufficiently stirred,
Dosage occurs for 1.0~1.5%, 5~10 minutes post-polymerizations of monomer weight, and system temperature can rise to from 20~25 DEG C
40~45 DEG C, and white polystyrene emulsion is quickly formed, polymerisation terminates within half an hour, and now styrene consumes substantially
To the greatest extent；
3) different amounts of second of monomer methyl acrylate is added, monomer is absorbed by polystyrene emulsion quickly, then adds the
Two batches of potassium peroxydisulfates, dosage are the 1% of methyl acrylate weight, and 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 PMA block；
4) acrylamide of different weight is added after the second the end of the step as second of monomer, over cure is added after its dissolving
Sour potassium, dosage are the 1% of acrylamide weight, and restarting is reacted after of short duration induction period, and the viscosity of system substantially increases
Greatly, the amphipathic copolymer with polystyrene and polyacrylamide block, above-mentioned emulsion product methanol extraction are finally obtained
Solid product is all obtained afterwards.
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| CN106432648B (en) * | 2016-10-22 | 2018-10-23 | 宁波大学 | A kind of environment-friendly preparation method thereof of vinyl chloride/N, N- dimethacrylamide copolymer |
| CN106496466B (en) * | 2016-10-22 | 2018-08-07 | 宁波大学 | A kind of Green Chemistry preparation method of vinyl chloride/butyl acrylate copolymer |
| CN109134735B (en) * | 2018-04-18 | 2021-04-30 | 宁波大学 | High-molecular method of disperse scarlet dye S-BWFL |
| CN109957047B (en) * | 2019-02-27 | 2021-11-16 | 宁波大学 | Polyhydroxy dodecahydrazide initiator and use method thereof |
| CN109879782B (en) * | 2019-02-27 | 2021-06-25 | 宁波大学 | Benzoyl hydrazine monosulfonic acid sodium initiator and preparation and use methods thereof |
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|---|---|---|---|---|
| US4762628A (en) * | 1985-03-12 | 1988-08-09 | Ciba-Geigy Corporation | Nitrogen-containing additives for non-aqueous functional fluids |
| CN101638852A (en) * | 2009-08-31 | 2010-02-03 | 温州大学 | Leveling and deepening fixing agent and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762628A (en) * | 1985-03-12 | 1988-08-09 | Ciba-Geigy Corporation | Nitrogen-containing additives for non-aqueous functional fluids |
| CN101638852A (en) * | 2009-08-31 | 2010-02-03 | 温州大学 | Leveling and deepening fixing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of Three Novel Laurylamine-Derived Long-Chain Alkyl Bonding Agents and Their Interactions with RDX;Yun-fei Liu et al.;《Yun-fei Liu et al.》;20121231;第37卷;第69-76页 * |
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