CN105884937B - A kind of anion surface active initiator and preparation method thereof - Google Patents
A kind of anion surface active initiator and preparation method thereof Download PDFInfo
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- CN105884937B CN105884937B CN201510344703.0A CN201510344703A CN105884937B CN 105884937 B CN105884937 B CN 105884937B CN 201510344703 A CN201510344703 A CN 201510344703A CN 105884937 B CN105884937 B CN 105884937B
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Abstract
The present invention is on a kind of anion surface active initiator and preparation method thereof.A kind of tertiary amine compound containing azochlorosulfonate acid anion and dodecyl of synthesis, itself it is 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, the multiphase of styrene and butyl acrylate and styrene and acrylamide is successively triggered to concatenate polymerization 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, power 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 anion surface active initiator and its change
Length of schooling Preparation Method, the new initiator can be used for the green syt of polyolefin macromolecular material.
Background technology
Polyolefin is the very important high polymer material of a class, is had a wide range of applications in every field.These materials one
As be all to be obtained olefinic monomer homopolymerization or copolymerization by initiator, different according to polymerization occasion, it is molten that initiator can be divided into oil
Property and water-soluble two major class, the polymerization of oil-soluble and water-soluble monomer is corresponded to respectively, under the special occasions of emulsion polymerization, is borrowed
The peptizaiton of cosurfactant, water soluble starter can also trigger the poly- of oil-soluble monomer by diffusing into micella
Close.In existing high molecular polymerization technology, a kind of few initiators can trigger under same reaction occasion in aqueous phase
Monomer polymerization again the monomer in oil phase can be triggered to polymerize, the barrier of the use Presence of an interface of initiator in heterogeneous system, if
This restriction can be broken, the polymerisation in different phases is connected in series, realize initiation across mutually cooperateing with, can be to polyolefin
Huge impetus is played in the synthesis of family macromolecule.In the evolution of high polymer material, people are to macromolecular structure
Design is often done one's utmost, but seems not enough to the improvement of initiator, although the invention of living radical polymerization technique can make
The synthesis of block copolymer becomes simple, but these active free radical polymerizations can only typically be carried out in organic phase, it is impossible to accomplish
Across phase-polymerization, synthesized block polymer feature is not enough, and application value is limited, so far can not large-scale popularization, tradition initiation
The function deficiency of agent has become a short slab of polyolefin macromolecular Materials, therefore in terms of initiator functional promotion
Still there are many researchs to do.
Realize that the key of multiphase concatenation polymerization methodses is the strict positioning of initiator, initiator there itself have to be surface
The characteristic of activating agent, it can just be in the interface of aqueous phase and oil phase, be possible to get through the resistance of the polymerisation of water/oil two-phase
Every, realize multiphase concatenate.On the other hand, as initiator, it must also can produce free radical, for general initiator, one
Individual molecule can only disposably produce free radical, control of like this just having no idea, and can realize that controllable drawn with the chain of rings
The initiator of characteristic is sent out, specific method is exactly that free radical is produced using redox reaction, and reducing agent therein is to trigger
Agent main body --- amphipathic trimethylamine molecule, oxidant is water miscible K2S2O8, redox reaction carries out at normal temperatures,
Nitrogen-atoms on tertiary amine loses an electronics, forms radical cation, then former in adjacent carbons by Intramolecular electron transfer
Hydrogen ion is ionized out on son, carbon radicals are formed, nitrogen-atoms can be with repeated oxidation, until on adjacent carbon atom after being reduced
Hydrogen all consumption (as shown in Figure 2).Free radical produced by initiator is exactly interface free radical, and it can trigger the polymerization of oil phase
Reaction, can also trigger the polymerisation of aqueous phase, what the hydrophobic chain and hydrophilic chain generated was connected together, here it is multiphase string
Polymerization is connect, its general principle is as shown in Figure 3.
Involved in the present invention is a case as this new polymerization methodses, designed initiator be it is a kind of it is cloudy from
Sub- surface active initiator (as shown in Figure 1), it is in K2S2O8Under effect, free radical can be produced at normal temperatures, successfully triggered and dredged
The polymerization of aqueous monomer styrene, butyl acrylate and hydrophilic monomer acrylamide, obtain that other polymerization means are difficult to obtain is more
Block copolymer, and this polymerization methodses comply fully with the standard of Green Chemistry --- normal-temperature reaction, low energy consumption, without using having
Machine solvent, also without using other emulsifying agents.
The content of the invention
Primary technical problem to be solved by this invention is to provide a kind of anion surface active initiator, this initiator
With water/oil interface locating features, and by the redox reaction with potassium peroxydisulfate, the free radical produced at normal temperatures can be double
To water-soluble and oil-soluble monomer is triggered, multiphase concatenation polymerization is realized, segmented copolymer can be finally formed.
Another technical problem to be solved by this invention is to provide the preparation side of above-mentioned anion surface active initiator
Method, it is practical, easy to operate, it is easy to a large amount of to prepare.
Another technical problem to be solved by this invention is to provide a kind of above-mentioned anion surface active initiator in benzene
Concrete application in ethylene/butyl acrylate/acrylamide segmented copolymer preparation.
1st, the present invention solve technical scheme that primary technical problem used for：A kind of anion surface active initiator,
Its chemical constitution is as shown in figure 1, it is a kind of anion surfactant first, with emulsification, and in potassium peroxydisulfate
Free radical is produced under oxidation, can trigger oiliness or the polymerization of aqueous monomer in interface, thus it is a kind of advanced draws
Send out agent.
It is beneficial that this initiator can be positioned at the interface of water/oil two-phase, the energy with emulsive oily monomer
Power, thus no longer need to add other emulsifying agents, once 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 at normal temperatures react with potassium peroxydisulfate, interface free radical is produced, it is double
To the polymerization of aqueous 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, efficiency of initiation is high, and different monomers can be made to be gathered according to the order fed intake
Close, be conducive to the MOLECULE DESIGN of polyolefin macromolecular material.
2nd, the present invention solve the technical scheme that is used of another technical problem for：A kind of above-mentioned anion surface active draws
The preparation method of agent is sent out, its synthetic route is as shown in figure 4, its characterization step is：1) sodium sulfite is dissolved in water, it is made into 15~
20wt.% concentrated solutions, are placed in wide-mouth bottle, and excessive epoxychloropropane, sodium sulfite and epoxychloropropane are added at normal temperatures
Mol ratio in 1: 1.1~1: 1.2 scopes, normal-temperature reaction 12~15 hours, and often stir, obtain substantial amounts of clear crystal-
2- hydroxyl -3- chlorine propanesulfonates, yield is almost 100%, is washed after filtering with a small amount of ethanol, drying for standby；2) by lauryl amine
With ethylene glycol according to 1: 3.5~1: 4 weight than mixed dissolution, above-mentioned 2- hydroxyls -3- chlorine propanesulfonates are added, are dissolved by heating
And reacted with lauryl amine at a temperature of 75~80 DEG C, the mol ratio of lauryl amine and 2- hydroxyl -3- chlorine propanesulfonates is 1: 1.05~1
: 1.1 scopes, reaction is cooled to normal temperature after 2~3 hours, has white precipitate NaCl precipitations, pours the mixture into clear water, inner salt
Type product is separated out with white precipitate, filters and removing solvent ethylene glycol, accessory substance NaCl and a small amount of unreacted are washed with clear water
2- hydroxyl -3- chlorine propanesulfonates, after drying obtain white solid propane sulfonic acid lauryl amine inner salt；3) by above-mentioned inner salt with
The mixing of NaOH equimolars, which is dissolved in methanol, to be placed in autoclave, and the weight ratio of inner salt and methanol is added in 1: 3~1: 4 scopes
The expoxy propane that 1.3~1.5 times of inner salt molal quantity, reacts 2~3 hours at 40~50 DEG C after closing, puts product after cooling
Dry to remove methanol under normal temperature in vacuum, the block of white is obtained, here it is final product.
It is beneficial that the preparation of 2- hydroxyl -3- chlorine propanesulfonates is very simple, and yield is high, cost is low, can be with
It is dissolved in ethylene glycol, is conducive to same organic amine to react, introduces azochlorosulfonate acid anion；
It is beneficial that in second step preparation, product propane sulfonic acid lauryl amine inner salt is water insoluble, washing can be passed through
Method separation product, it is ensured that purity.
3rd, the present invention solve the technical scheme that is used of another technical problem for：Above-mentioned anion surface active initiator
Application process in polyolefin synthesis, its characterization step is：1) it is anion surface active initiator is soluble in water, concentration one
As in 2.5~3.0 ‰ scopes, the consumption of initiator is usually the 2.5~3.0% of the first monomer weight；2) by oil-soluble monomer
Be added in emulsion, added after being sufficiently stirred for potassium peroxydisulfate solid powder (generally put into monomer weight 1.0~
1.5%), about 5~10 minutes post-polymerizations occur, and system temperature has risen, and quickly forms polymer emulsion；3) add
Enter second of monomer, if second comonomer is oil-soluble, then the Polymer absorption that it can have been formed, add second batch
After potassium peroxydisulfate, polymerisation restarts, and the diameter of emulsion particle becomes big, finally obtains the copolymer of many blocks；If the
Two kinds of monomers are water miscible, then after same operation, obtain amphipathic block copolymer.
It is beneficial that because free radical is only produced 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 being 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 of polymer is easily controlled, a variety of blocks can be implemented according to actual requirement
Random collocation；3) polymeric reaction condition is gently controllable, consumes energy low, without using other organic solvents and emulsifying agent, products 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 anion surface active initiator：
1st, sodium sulfite is dissolved in water, is made into 15~20wt.% concentrated solutions, is placed in wide-mouth bottle, added at normal temperatures
The mol ratio of the epoxychloropropane of amount, sodium sulfite and epoxychloropropane is in 1: 1.1~1: 1.2 scopes, normal-temperature reaction 12~15
Hour, and often stir, substantial amounts of clear crystal -2- hydroxyls -3- chlorine propanesulfonates are obtained, yield is almost 100%, after filtering
Washed with a small amount of ethanol, drying for standby；
2nd, by lauryl amine and ethylene glycol according to 1: 3.5~1: 4 weight than mixed dissolution, add above-mentioned 2- hydroxyls -3-
Chlorine propanesulfonate, dissolves by heating and is reacted with lauryl amine at a temperature of 75~80 DEG C, lauryl amine and 2- hydroxyl -3- chlorine propanesulfonates
Mol ratio in 1: 1.05~1: 1.1 scopes, reaction is cooled to normal temperature after 2~3 hours, there is white precipitate NaCl precipitations, will be mixed
Compound is poured into clear water, and interior salt form product is separated out with white precipitate, filters and removing solvent ethylene glycol, accessory substance are washed with clear water
NaCl and a small amount of unreacted 2- hydroxyls -3- chlorine propanesulfonates, are obtained in white solid propane sulfonic acid lauryl amine after drying
Salt, yield 78~86%；
3rd, above-mentioned inner salt is mixed to be dissolved in methanol with NaOH equimolars and be placed in autoclave, the weight of inner salt and methanol
Than in 1: 3~1: 4 scopes, adding the expoxy propane of 1.3~1.5 times of inner salt molal quantity, after closing at 40~50 DEG C reaction 2~
3 hours, product is placed in vacuum under normal temperature after cooling and dried to remove methanol, the block of white is obtained, here it is finally
Product, yield 90~96%.
The use of anion surface active initiator is carried out by following operating procedure：
A. 1.5g anion surface active initiators are dissolved in 500mL water, are made into emulsion, concentration typically 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 for
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 terminates typically within half an hour,
Now styrene exhausts substantially；
C. second of monomer butyl acrylate of different quality is added, monomer is absorbed by polystyrene emulsion quickly, then
Second batch potassium peroxydisulfate (weight of butyl acrylate 1.0%) is added, polymerisation restarts, on system temperature starts again
Rise, the diameter of emulsion particle becomes big, finally obtains the copolymer containing polystyrene and butyl polyacrylate block；
D. the acrylamide of different weight is added after the second the end of the step as second of monomer, is added after after its dissolving
Potassium peroxydisulfate (the 1.0% 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, to the reactant mixture methanol extraction of unit volume after polymerizeing every time, is removed that may be present
Small-molecule substance, is weighed after the scrubbed drying of resulting polymer, just obtains polymer output, and polymerization for the first time obtains polyphenyl
The yield of ethene, obtains the yield of copolymer, thus extrapolates the quality group of two kinds of blocks in copolymer after second of polymerization
Into than M1/M2, and rate of charge m1/m2The mass ratio of the two kinds of monomers added in exactly testing.Each second comonomer is carried out
Four combined polymerizations are tested, and resulting the experimental results are shown inthe following table, it can be found that rate of charge has very well with ratio of components from table
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 is compareed with the ratio of components of copolymer
Brief description of the drawings
The chemical constitution of Fig. 1 anion surface active initiators.
Fig. 2 Redox Initiator principles.
Fig. 3 multiphases concatenate polymerization methodses schematic diagram.
The synthetic route of Fig. 4 anion surface active initiators.
Claims (2)
1. a kind of anion surface active initiator, the structural formula of the initiator is：
It is characterized in that redox reaction can at normal temperatures occur with potassium peroxydisulfate for the tertiary amine unit in structure, activity is produced certainly
By base；Described anion surface active initiator is distributed in water/oil interface because having emulsifying agent function concurrently, thus it is produced from
By base aqueous phase can be triggered to trigger the olefinic monomer of oil phase again, occur Raolical polymerizable.
2. the preparation method of anion surface active initiator described in a kind of claim 1, it is characterised in that step is followed successively by：
1) by lauryl amine and ethylene glycol according to 1: 3.5~1: 4 weight than mixed dissolution, add 2- hydroxyl -3- chlorine propane sulfonic acid
Sodium, dissolves by heating and is reacted with lauryl amine at a temperature of 75~80 DEG C, the mol ratio of lauryl amine and 2- hydroxyl -3- chlorine propanesulfonates
In 1: 1.05~1: 1.1 scopes, reaction is cooled to normal temperature after 2~3 hours, pours the mixture into clear water, interior salt form product with
White precipitate is separated out, and filters and removing impurity is washed with clear water, white solid propane sulfonic acid lauryl amine inner salt is obtained after drying；
2) inner salt obtained by step (1) is mixed to be dissolved in methanol with NaOH equimolars and be placed in autoclave, inner salt and methanol
Weight ratio adds the expoxy propane of 1.3~1.5 times of inner salt molal quantity in 1: 3~1: 4 scopes, anti-at 40~50 DEG C after closing
Answer 2~3 hours, product is placed in vacuum under normal temperature after cooling and dried to remove methanol, obtained white block is most
Whole product.
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| CN109134726B (en) * | 2018-04-18 | 2021-04-30 | 宁波大学 | Phthalocyanine dye high-molecular method |
| CN109134770B (en) * | 2018-04-18 | 2021-09-21 | 宁波大学 | High-molecular method of active brilliant red dye K-2BP |
| CN111320551B (en) * | 2019-01-15 | 2021-04-27 | 山东大学 | Secondary amide diamine quaternary ammonium salt amphoteric asphalt emulsifier and preparation 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1817852A (en) * | 2006-03-21 | 2006-08-16 | 华东理工大学 | Duplex surfactant and production thereof |
| CN101628884A (en) * | 2009-07-01 | 2010-01-20 | 大庆高新区华龙祥化工有限公司 | Preparation method of ampholytic surfactant and application thereof in tertiary oil recovery |
| CN102491922A (en) * | 2011-12-02 | 2012-06-13 | 西南石油大学 | Bishydroxyl sulfoacid betaine surface active agent and synthesis method thereof |
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| JPS6369990A (en) * | 1986-09-10 | 1988-03-30 | Kao Corp | Production of acid type aminosulfonic acid |
| JPH0674511B2 (en) * | 1986-10-02 | 1994-09-21 | 花王株式会社 | Method for producing amphoteric surfactant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1817852A (en) * | 2006-03-21 | 2006-08-16 | 华东理工大学 | Duplex surfactant and production thereof |
| CN101628884A (en) * | 2009-07-01 | 2010-01-20 | 大庆高新区华龙祥化工有限公司 | Preparation method of ampholytic surfactant and application thereof in tertiary oil recovery |
| CN102491922A (en) * | 2011-12-02 | 2012-06-13 | 西南石油大学 | Bishydroxyl sulfoacid betaine surface active agent and synthesis method thereof |
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