CN109942729A - A kind of amphipathic acethydrazide initiator and its preparation and application method - Google Patents
A kind of amphipathic acethydrazide initiator and its preparation and application method Download PDFInfo
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- CN109942729A CN109942729A CN201910246277.5A CN201910246277A CN109942729A CN 109942729 A CN109942729 A CN 109942729A CN 201910246277 A CN201910246277 A CN 201910246277A CN 109942729 A CN109942729 A CN 109942729A
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Abstract
The present invention relates to a kind of amphipathic acethydrazide initiator and its preparation and application methods.Synthesize a kind of compound containing octadecyl chain and hydrazides, with surfactant character, with potassium peroxydisulfate redox reaction can occur for hydrazides at normal temperature simultaneously, it can be repeated several times and generate free radicals, flexibly control multiphase concatenation polymerization, sequentially cause styrene and methyl methacrylate and styrene and hydroxy-ethyl acrylate in water/oil interface, obtain segmented copolymer, experiments have shown that the feed ratio of 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 mode is mildly controllable, low energy consumption, without other organic solvents and emulsifier, 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 amphipathic acethydrazide initiator and its preparation
With application method, which can be used for the green syt of polyolefin macromolecular material.
Background technique
Polyolefin is a kind of very important commodity polymer material, and structure is adjustable, is widely used.These materials are generally all
It is to be obtained olefinic monomer homopolymerization or copolymerization by radical initiator, different according to polymerization occasion, initiator can be divided into oil
Dissolubility and water-soluble two major classes, respectively correspond the polymerization of oil-soluble and water-soluble monomer.Common initiator is a kind of energy
The compound generated free radicals, such as oil-soluble peroxide, azo-initiator and water-soluble persulfate, initiator
Use have to match with specific polymerization reaction environment, thus they often only play a booster action, not
It is the core of polymerization technique.In recent years, living radical polymerization technique obtains significant progress, to the initiation method of free radical into
It has gone improvement, thus the synthesis of block copolymer can be made to become simple and convenient, but these active free radical polymerizations generally can only
It is carried out in organic phase, can not accomplish the leap from oily phase to water phase, its structural variability of synthesized block polymer is not
Very strong, practical application value is limited, so far can not large-scale popularization.If the structure and function of initiator is designed and is changed
It makes, initiator can be made to become the core content of polymerization technique completely, thus polymerization reaction can be made easy to operate, cost drop
It is low, while polymer material obtained has stronger function, wider application prospect.Novel initiator should have
Two kinds of characteristics: first is that initiator can be located in the interface of water phase with oily phase, the free radical that it is generated in this way can make in water phase
Monomer polymerization and monomer polymerization in oily phase can be made, break the restriction of multi phase interface；Second is that an initiator molecule is necessary
It can repeatedly generate free radicals, generate controllable connecting ring type and cause, so polymerization reaction can realize that multiphase concatenates, i.e.,
Different polymer blocks are connected with an initiator molecule, form segmented copolymer.In the development of high molecular material
Cheng Zhong, people often do one's utmost to the design of macromolecular structure, but seem insufficient to the improvement of initiator, in fact cause
The design of agent is also a very important link, it can bring very big convenience to the MOLECULE DESIGN of high molecular material.
Realize that the most important condition of multiphase concatenation polymerization methods is the stringent positioning of initiator, only when initiator has table
When the characteristic of face activating agent, molecule can be in the interface of water phase with oily phase, it is possible to it is poly- to cause water/oil two-phase concatenation
It closes.On the other hand, initiator should be controllable in advance as free radical generating source, i.e., is repeatedly produced from by the design of chemical reaction
By base, this point is closely similar with radical living polymerization.Only exist the difference is that the reactive species of radical living polymerization are general
One specific place generates, and limits chemical design in this way.Free radical may be implemented completely using redox reaction to exist
Different places repeats to generate, and wherein reducing agent is organic compound, and oxidant is water-soluble inorganic compound such as K2S2O8。
The alkylated nitrogen-atoms of one of them of single hydrazide kind compound still has reproducibility, and redox reaction first occurs at this
On a nitrogen-atoms, it is initially formed radical cation after being oxidized, and then powers in adjacent carbon atom and separates out hydrogen ion, is formed
Carbon radicals, nitrogen-atoms can be with repeated oxidations, until all ionization of the hydrogen on adjacent carbon atom, triggering mechanism after being reduced
As shown in Figure 2.Although the initiator of hydrazide structure and trimethylamine class compound have similar redox reaction characteristic,
It is that hydrazide kind compound is more stable than organic amine compound, contact with air will not be oxidized for a long time, while hydrazide structure
Initiator efficiency of initiation it is higher, it is not easy to generate gel phenomenon in the course of the polymerization process.
The present invention relates to a case of this new polymerization methods, designed initiator is a kind of amphipathic acetyl
Hydrazine initiator, it is in K2S2O8It under effect, can generate free radicals at normal temperature, successfully cause oiliness monomer styrene, methyl-prop
The polymerization of e pioic acid methyl ester and hydrophilic monomer hydroxy-ethyl acrylate obtains the segmented copolymer that other polymerization means are difficult to,
And this polymerization methods comply fully with Green Chemistry one normal-temperature reaction of standard low energy consumption, organic solvent-free, without other surfaces
Activating agent.
Summary of the invention
Primary technical problem to be solved by this invention is to provide a kind of amphipathic acethydrazide initiator, this initiator tool
There are water/oil interface locating features, and by the redox reaction with potassium peroxydisulfate, the free radical generated at normal temperature can be two-way
Cause water-soluble and oil-soluble monomer, realizes 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 amphipathic acethydrazide initiator,
It is practical, easy to operate, is easy to largely prepare.
Another technical problem to be solved by this invention is to provide the above-mentioned amphipathic acethydrazide initiator of one kind in benzene second
Concrete application in alkene/methyl methacrylate/acrylic acid hydroxyl ethyl ester segmented copolymer preparation.
1, the present invention solves technical solution used by primary technical problem are as follows: a kind of amphipathic acethydrazide initiator,
Chemical structure can be dispersed in water, together well as shown in Figure 1, it is a kind of organic compound with amphiphilic character
When again can affine oil-soluble monomer generate free radicals initiation water/oil two-phase monomer under the oxidation of potassium peroxydisulfate and gather
It closes.
It is beneficial that initiator can react at normal temperature with potassium peroxydisulfate, interface free radical, two-way initiation water are generated
Property and oiliness monomer polymerization, synthesize segmented copolymer by multiphase concatenation；
It is beneficial that this initiator can be repeatedly produced from closing on carbon atom by constantly oxidation nitrogen-atoms
It polymerize various of monomer according to the sequence to feed intake by base so as to flexile control polymerization reaction, is conducive to gather
The MOLECULE DESIGN of Olefin Polymer；
It is beneficial that this amphipathic acethydrazide initiator has preferable stability, contacted for a long time with air
Not oxidized, obtained polymer is not allowed to be also easy to produce gel after initiated polymerization.
2, the present invention solves technical solution used by another technical problem are as follows: a kind of above-mentioned amphipathic acethydrazide initiation
The preparation method of agent, synthetic route is as shown in figure 3, its characterization step are as follows: 1) by stearic acid glycidyl ester and equimolar number
Acethydrazide be dissolved in dehydrated alcohol jointly, the mass ratio of stearic acid glycidyl ester and ethyl alcohol is controlled in 1: 4.5~1: 5 models
It encloses, so that reaction solution is flowed back under stiring 2~3 hours, be cooled to room temperature after the reaction was completed；2) it is added and shrinks in Xiang Shangshu reaction solution
The molar ratio of glycerol, glycidol and acethydrazide is 1: 1, controls reacting liquid temperature under stiring in 35~40 DEG C of ranges, reaction 3
It is cooled to room temperature after~4 hours；3) above-mentioned reaction solution rotary evaporator is concentrated to remove ethyl alcohol, finally obtains white solid
Shape substance, the product are exactly amphipathic acethydrazide initiator, it can be dissolved in water well.
3, the present invention solves technical solution used by another technical problem are as follows: above-mentioned amphipathic acethydrazide initiator exists
Application method in polyolefin synthesis, characterization step is: 1) it is amphipathic acethydrazide initiator is soluble in water, it is dense to be made into quality
The aqueous solution in 1.0~1.5 ‰ ranges is spent, the dosage of initiator is the 1.0~1.5% of the first monomer weight；2) by oil-soluble
Monomer is added in aqueous solution, after being sufficiently stirred be added potassium peroxydisulfate solid powder, dosage be investment monomer weight 1.0~
1.5%, 5~dispersion polymerization occurs after ten minutes, system temperature is risen, and quickly forms polymer dispersion liquid；3)
Second of monomer is added, if second comonomer is Polymer absorption oil-soluble, that it can have been formed, is added second
After criticizing potassium peroxydisulfate, polymerization reaction restarts, and polymer beads become large-sized, and finally obtains the copolymer of more blocks；Such as
Second of monomer of fruit is water-soluble, then obtaining amphiphilic block copolymer after similarly operating.
It is beneficial that efficiency of initiation is high, and monomer concentration is high in oily phase since free radical only generates at interface, thus
Polymerization reaction is fast, high conversion rate, and monomer can be sequentially added into polymerization process, is very easy to the composition and knot of control polymer
Structure；
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) multiphase concatenation aggregation scheme, i.e., a kind of initiation may be implemented using new initiator
Agent can complete the polymerization of various ways；2) it is easy to control the composition and structure of polymer, can be implemented according to actual requirement more
The random collocation of kind block；3) it is easy to introduce phosphonate radical functional group in the polymer by using the initiator；4) it polymerize
Reaction condition is mildly controllable, low energy consumption, does not have to other organic solvents and emulsifier, and products pure complies fully with Green Chemistry
It is required that.
Specific embodiment
The feed ratio of polymerization reaction is compareed with the ratio of components of copolymer
Detailed description of the invention
The chemical structure of the amphipathic acethydrazide initiator of Fig. 1.
Fig. 2 Redox Initiator principle.
The synthetic route of the amphipathic acethydrazide initiator of Fig. 3.
Claims (2)
1. a kind of preparation method of amphipathic acethydrazide initiator, it is characterised in that the structural formula of the initiator are as follows:
The preparation method of the amphipathic acethydrazide initiator, it is characterised in that step is successively are as follows:
1) acethydrazide of stearic acid glycidyl ester and equimolar number is dissolved in jointly in dehydrated alcohol, stearic acid glycidyl ester
It controls with the mass ratio of ethyl alcohol in 1: 4.5~1: 5 ranges, reaction solution is made to flow back under stiring 2~3 hours, it is cold after the reaction was completed
But to room temperature；
2) it is added glycidol in Xiang Shangshu reaction solution, the molar ratio of glycidol and acethydrazide is 1: 1, and control is anti-under stiring
Answer liquid temperature in 35~40 DEG C of ranges, reaction is cooled to room temperature after 3~4 hours；
3) above-mentioned reaction solution rotary evaporator is concentrated to remove ethyl alcohol, finally obtains white solid substance, the product is just
It is amphipathic acethydrazide initiator, it can be dissolved in water well.
2. a kind of application method of amphipathic acethydrazide initiator described in claim 1, step is successively are as follows:
1) the amphipathic acethydrazide initiator of 1.0g is dissolved in 1000mL water, is made into mass concentration in the water of 1.0~1.5 ‰ ranges
Solution；
2) 80g oil-soluble monomer styrene is added in aqueous solution, 0.8g potassium peroxydisulfate solid powder is added after being sufficiently stirred,
Its dosage be put into monomer mass 1.0~1.5%, 5~occur dispersion polymerization after ten minutes, system temperature can from 20~
25 DEG C rise to 40~45 DEG C, and quickly form white polystyrene dispersion liquid, and polymerization reaction terminates within half an hour, at this time benzene
Ethylene exhausts substantially；
3) different amounts of second of monomers methyl methacrylate is added, monomer is absorbed by granules of polystyrene quickly, then plus
Enter second batch potassium peroxydisulfate, dosage is the 1% of methyl methacrylate quality, and polymerization reaction restarts, and system temperature is again
It begins to ramp up, polymer particle sizes become larger, and finally obtain the copolymerization containing polystyrene and MPM methyl polymethacrylate block
Object；
4) hydroxy-ethyl acrylate of different weight is added after second step as second of monomer, is added after its dissolution
Potassium peroxydisulfate, dosage are the 1% of hydroxy-ethyl acrylate quality, and restarting is reacted after of short duration induction period, system
Viscosity significantly increases, and finally obtains the amphipathic copolymer with polystyrene and hydroxyethyl acrylate block, above-mentioned emulsion
Solid product is all obtained after product methanol extraction.
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| CN103038195A (en) * | 2010-06-22 | 2013-04-10 | 乌尔里希·迪茨 | Device and method for solubilizing, separating, removing and reacting carboxylic acids in oils, fats, aqueous or organic solutions by means of micro- or nanoemulsification |
| CN104804125A (en) * | 2015-04-16 | 2015-07-29 | 佛山市顺德区巴德富实业有限公司 | Adipic dihydrazide modified acrylic ester emulsion for removing formaldehyde and preparation method of emulsion |
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2019
- 2019-02-27 CN CN201910246277.5A patent/CN109942729B/en active Active
Patent Citations (5)
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|---|---|---|---|---|
| US3293325A (en) * | 1962-12-08 | 1966-12-20 | Canadian Ind | Copolymers of vinyl acetate with monoallylesters of polycarboxylic or hydroxy carboxylic acids with an aminoplast resin |
| US20020065380A1 (en) * | 2000-09-28 | 2002-05-30 | Dominique Charmot | Emulsion living-type free radical polymerization, methods and products of same |
| CN103038195A (en) * | 2010-06-22 | 2013-04-10 | 乌尔里希·迪茨 | Device and method for solubilizing, separating, removing and reacting carboxylic acids in oils, fats, aqueous or organic solutions by means of micro- or nanoemulsification |
| CN102030860A (en) * | 2010-10-29 | 2011-04-27 | 浙江菲达中科精细化学品有限公司 | Self-crosslinking acrylic emulsion and preparation process thereof |
| CN104804125A (en) * | 2015-04-16 | 2015-07-29 | 佛山市顺德区巴德富实业有限公司 | Adipic dihydrazide modified acrylic ester emulsion for removing formaldehyde and preparation method of emulsion |
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| DEKA, H: "Graft Copolymerization of Methylmethacrylate onto Muga silk fiber using a new initiator system K2S2O8/NH2-NH2 center dot H2O", 《JOURNAL OF POLYMER MATERIALS》 * |
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