CN106432649A - Green preparation method of vinyl chloride/isoprene copolymer - Google Patents
Green preparation method of vinyl chloride/isoprene copolymer Download PDFInfo
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- CN106432649A CN106432649A CN201610938503.2A CN201610938503A CN106432649A CN 106432649 A CN106432649 A CN 106432649A CN 201610938503 A CN201610938503 A CN 201610938503A CN 106432649 A CN106432649 A CN 106432649A
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- vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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Abstract
The invention relates to a green preparation method of a vinyl chloride/isoprene copolymer as a thermoplastic elastomer. The preparation method is copolymer synthetic technology formed based on water/oil interfacial free radical polymerization. The preparation method is characterized by specially using a gemini surface active initiator to carry out redox reaction with potassium persulfate under normal temperature, repeatedly generating free radicals on the interfaces for multiple times and triggering independent polymerization reaction between vinyl chloride and isoprene and connecting the two chain segments together in series by initiator molecules, thus forming the multiblock polymer. Experiments prove that when the pH value of the aqueous medium is 4-4.5, the feed ratio of monomers is quite consistent with the component ratio of the copolymer; the content of the isoprene chain segment in the copolymer is adjustable in the range of 10-42wt.%; the polymerization reaction in such a mode is mild and controllable in conditions, is low in energy consumption and dispenses with other organic solvents and emulsifiers; the product is pure and completely meets the requirements of green chemistry.
Description
Technical field
The present invention relates to synthesis of polymer material technical field, especially a kind of system of vinyl chloride/isoprene copolymer
Preparation Method, this copolymer is a kind of thermoplastic elastomer (TPE), and its advanced preparation method meets the requirement of Green Chemistry.
Background technology
With developing rapidly of modern science and technology and society, people are to the performance requirement more and more higher of macromolecular material and day
Become variation, multifunction, and single polymer is often difficult to meet the needs of people, and the modification to macromolecular material seems non-
Often important.Thermoplastic elastomer (TPE) (TPE) is the elasticity that a class shows rubber at normal temperatures, plasticization molding again under high temperature, plus
The novel high polymer elastomeric material of work function admirable, it has and is not required to sulfuration, easy to process, low cost, can be recycled
Etc. a series of technology economy advantages, it is a contemporary synthetic rubber field development class product faster.
Polrvinyl chloride (PVC) is a kind of general-purpose plastics, and it is cheap, yield is big, application is wide, and has fire-retardant, resistance to molten
The characteristic such as agent, resistance to ozone, chemical stability be good, has been widely used in national economy every profession and trade.Polyvinyl chloride thermoplastic elastomehc
Gonosome (PVC-TPE) is the elastomeric material based on PVC, has that compression set is little, high temperature conformality is good, resilience
The characteristic such as greatly, ageing-resistant, oil resistant, bending fatigue strength be high, cheap, application is increasingly extensive.Existing PVC-TPE preparation side
Method all biases toward physical means, can be divided into and elastomer blended, introducing crosslinked structure, high relative molecular weight polrvinyl chloride plasticising 3
Kind, vinyl chloride is the relatively low monomer of a polymerization activity, typically little and other olefinic monomer copolymerization, thus greatly limit
The development space of its chemical modification.Water/oil two-phase interface polymerization technique can fundamentally crack this limitation of the technology, makes various
The synthesis of olefin copolymer becomes convenient, and meets Green Chemistry and require.
That realizes interfacial polymerization it is critical only that using double type surface active initiator as shown in Figure 1, at this initiator
At the interface of aqueous phase and oil phase, polyreaction biphase for water/oil can be connected in series by it, this amphipathic trimethylamine molecule
Can be with water miscible K2S2O8Constitute redox initiation system, by repeated Intramolecular electron transfer in nitrogen-atoms
Free radical is formed on adjacent carbon atom, interface free radical can cause the polyreaction of oil phase, also can cause the polymerization of aqueous phase
Reaction, as long as adding different monomers in a certain order it is possible to independent cause polymerization, does not interfere with each other, because polymerization is anti-
The spike answered both is from same initiator molecule, so what the polymer chain being formed was connected together, its ultimate principle
As shown in Fig. 2 it should be noted that, in order to ensure the smooth enforcement of copolyreaction, the compound mode of comonomer must with draw
The pH value of the structure and aqueous media of sending out agent matches.Polyisoprene is a kind of relatively low polymer elasticity of vitrification point
Rigid polyvinyl chloride chain can be linked together with flexible polyisoprene chain by above-mentioned polymerization methodses, be formed by body
Thermoplastic elastomer (TPE), can overcome the incompatible problem of two kinds of polymer completely.
Involved in the present invention is a case of this novel polymerizable mode, and initiator used is a kind of special construction
Double type surface active initiator, it is in K2S2O8Under effect, free radical can be produced at normal temperatures, live there is no additional surface
Cause the polymerization of hydrophobic vinyl chloride, isoprene respectively, obtain that other polymerization means are difficult to obtain is many in the presence of property agent
Block copolymer, this is a kind of new thermoplastic elastomer of polyvinyl-chloride, and this polymerization methodses comply fully with Green Chemistry
Standard --- normal-temperature reaction energy consumption is low, organic solvent-free, no other surfactant.
Content of the invention
Primary technical problem to be solved by this invention is to provide a kind of water/oil two-phase interface radical polymerization technique, this
The feature planting polymerization technique is to produce free radical under room temperature in specific water/oil two-phase interface, can cause different alkene lists
Body realizes each independent polymerization, and is concatenated multiple segments by initiator molecule, forms new copolymer.
Another technical problem to be solved by this invention is to provide double type necessary to the radical polymerization of above-mentioned interface
Surface active initiator, the function of its existing surfactant, redox initiation system can be formed with potassium peroxydisulfate, normal again
Temperature is lower to cause various polymerizing olefin monomers.
Another technical problem to be solved by this invention is using above-mentioned interface radical polymerization mode and specific
Surface active initiator, provides a kind of concrete grammar preparing vinyl chloride/isoprene segmented copolymer.
1st, the technical scheme that the primary technical problem of present invention solution is adopted is：A kind of water/oil two-phase interface radical polymerization
Conjunction technology, as shown in Fig. 2 it is different from the general polyreaction causing in aqueous phase or oil phase, it is a kind of to its ultimate principle
It is positioned the free radical initiation method of two-phase interface, the polyreaction complete independently of aqueous phase, oil phase can be made, polymeric chain can be made again
Section is serially connected on a kind of initiator.
It is beneficial that different monomers can with homopolymerization mode each complete independently, do not interfere with each other, but final obtain
Be many blocks copolymer；
It is beneficial that the composition of copolymer can control simply by the rate of charge of monomer, it is to avoid because of list
The impact that body activity difference forms to copolymer；
It is beneficial that monomers different for each attribute can be formed copolymer by this technology, various for synthesizing
Copolymer provide extensive feasibility.
2nd, the technical scheme that the present invention solves that another technical problem adopted is：A kind of double type surface active initiator
Its molecular structure is as shown in Figure 1.
It is beneficial that this initiator can be positioned at the biphase interface of water/oil, there is the energy of emulsive oily monomer
Power, thus it is no longer necessary to add other emulsifying agents, after causing polymerization, it just becomes a part for polymeric material, no
Emulsifying agent leakage problem can be produced, the performance of polymeric material will not be had a negative impact；
It is beneficial that the tertiary amine in initiator can be reacted at normal temperatures with potassium peroxydisulfate, produce interface free radical, double
To causing aqueouss and the polymerization of oiliness monomer, concatenate to synthesize segmented copolymer by multiphase；
It is beneficial that this initiator passes through continuous oxidation nitrogen-atoms repeatedly can produce free radical on alpha-carbon,
Show the feature that its chain of rings causes, flexibly can control polyreaction, so that various of monomer is polymerized in a certain order, very
Be conducive to the MOLECULE DESIGN of polyolefin macromolecular material.
3rd, the technical scheme that the present invention solves that another technical problem adopted is：Drawn using above-mentioned double type surface activity
Send out agent and prepare vinyl chloride/isoprene segmented copolymer concrete grammar, its characterization step is：1) double type surface activity is drawn
Send out agent soluble in water, concentration typically in 2.5～3.0 ‰ scopes, the consumption of initiator be usually vinyl chloride weight 2.5～
3.0%, the pH value adjusting aqueous solution, then will be water-soluble to faintly acid it is ensured that the emulsifying capacity of double type surface active initiator
Liquid is placed in airtight high-pressure reactor, then is passed through nitrogen into reactor to exclude the air of inside；2) by oil-soluble monomer
Vinyl chloride is injected in reactor, and (amount of potassium peroxydisulfate is generally to add potassium peroxydisulfate saturated solution after being sufficiently stirred under room temperature
Put into the 1.0～1.5% of monomer weight), post-polymerization occurs within about 5～10 minutes, and quickly forms polymer dispersion liquid,
Temperature of reaction system and pressure have risen, but gradually fall after rise after supercooling, and the polyreaction of first stage typically continues 0.5
～1 hour；3) add second monomer isoprene, the weight of isoprene and vinyl chloride ratio in 0.1～0.7 scope,
By swelling rapidly, after adding second batch potassium peroxydisulfate, polyreaction restarts the polrvinyl chloride being formed, the diameter of dispersed particle
Become big, reaction continues 1～2 hour, finally obtains granular thermoplastic elastomer (TPE), the composition of product can be by the throwing of monomer
Expect ratio to control.
It is beneficial that because free radical only produces at interface, oiliness monomer concentration is high, thus polyreaction is fast, turns
Rate 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 the polyreaction of vinyl chloride is carried out at normal temperatures, high pressure will not be produced, thus improve
The safety coefficient of operation；
It is beneficial that being added without other organic solvents it is not necessary to exacting terms in whole polymerization process, accord with completely
Close the requirement of Green Chemistry.
It is an advantage of the current invention that：1) the independent equal of various of monomer can be realized using new interface radical polymerization technique
Coalescence mutually concatenates, and is easily controlled composition and the structure of polymer；2) reactivity ratio, monomer physical difference are avoided to traditional copolymerization
The restriction of method, is conducive to preparing a greater variety of olefin copolymers, has significantly widened macromolecular material development space；3) it is polymerized
Reaction condition is gently controlled, low energy consumption, without other organic solvents and emulsifying agent, products pure, complies fully with Green Chemistry
Require.
Specific embodiment
With reference to embodiments the present invention is described in further detail.
Vinyl chloride/isoprene copolymer preparation is carried out by following operating procedure：
A. 1.5g double type surface active initiator is dissolved in 500mL water, concentration typically in 2.5～3.0 ‰ scopes, is drawn
The consumption sending out agent is usually the 2.5～3.0% of vinyl chloride weight, is adjusted water-soluble by the different amounts of acetic acid of addition or sodium phosphate
PH value (pH=9～9.5 of liquid；PH=7～7.5；PH=4～4.5), aqueous solution is placed in airtight high-pressure bottle, Xiang Rong
The air to exclude inside for the logical nitrogen in device；
B. 55g oil-soluble monomer vinyl chloride (boiling point is -13.4 DEG C) is injected in reactor, after being sufficiently stirred under room temperature
Addition potassium peroxydisulfate saturated solution (amount of potassium peroxydisulfate is generally and puts into the 1.0～1.5% of monomer weight), about 5～10 points
Clock post-polymerization occurs, and quickly forms polymer dispersion liquid, and system temperature and pressure have risen, and temperature rises typically not
More than 10 DEG C, gradually fall after rise after supercooling, the polyreaction of first stage typically continues 0.5～1 hour；
C. add different amounts of second monomer isoprene, the weight of isoprene and vinyl chloride is than in 0.1～0.7 model
Enclose, by swelling rapidly, after adding second batch potassium peroxydisulfate, polyreaction restarts the polrvinyl chloride having been formed, dispersible granule
The diameter of son becomes big, and reaction continues 1～2 hour, finally obtains granular thermoplastic elastomer (TPE), dry after fully being washed with clear water
Dry standby.
Product analysis：By compare twice after polyreaction monomeric charge weigh than the concordance with copolymer ratio of components
The actual effect of this initiator, the reactant mixture methanol extraction to unit volume after being polymerized every time, remove and be possible to deposit
Small molecule monomer, weigh after the scrubbed drying of obtained polymer, just obtain polymer output, polymerization for the first time obtains
Yield M of polrvinyl chloride1, after being polymerized for second, obtain yield M of copolymer1+M2, two kinds thus extrapolated in copolymer embedding
The quality ratio of components M of section2/M1, and rate of charge m2/m1It is exactly the mass ratio of the two kinds of monomers adding in experiment.Obtained experiment
Result is as shown in Figure 3.
The control of product composition：Experimental data shows, rate of charge is relevant with the relation of ratio of components and the pH value of polymerisation medium,
When pH value is in 4～4.5 scope, the relation of rate of charge and ratio of components substantially on the diagonal, illustrates each polyreaction all
Than more thoroughly that is to say, that the efficiency of initiation of initiator is higher.The M when pH value is in 7～7.5 scope2/M1With m2/m1Dependency is bent
Line deviates to below diagonal, and the cornerwise phenomenon of substantial deviation when pH value 9～9.5, illustrates in the basic conditions
The polymerization of isoprene is not very abundant, and this may be lifted with initiator emulsifying capacity in acid condition, and in alkaline bar
The emulsified ability of part declines relevant.But when pH value is less than 4, the protonation of initiator leads to redox reaction to be subject to
Resistance, the trigger rate of initiator substantially reduces, and is unfavorable for the carrying out of polyreaction, so the pH value of medium controls in 4～4.5 models
Enclose proper.
Brief description
The chemical constitution of Fig. 1 double type surface active initiator.
The ultimate principle of Fig. 2 water/oil two-phase interface radical polymerization.
The impact that the pH value of Fig. 3 medium forms to copolymer.
Claims (5)
1. a kind of new method preparing vinyl chloride/isoprene copolymer, it is different from suitable olefinic monomer in general sense
Random copolymerization, graft copolymerization and block copolymerization it is characterised in that Raolical polymerizable only draws at the biphase interface of water/oil
Send out, and so that two kinds of monomers of vinyl chloride and isoprene is polymerized respectively by the order feeding intake, and embedding by two kinds by initiator molecule
Section is serially connected, and constitutes new copolymer.
2. the Raolical polymerizable of interfacial initiation according to claim 1 is it is characterised in that double type table must be used
Face active initiator, that is, by surfactant and initiator two-in-one, it has structure as shown in Figure 1, energy and water
There is redox reaction in the potassium peroxydisulfate in phase, produce free radical over and over again, in medium pH on different carbon atoms
The good efficiencies that=4～4.5 scopes have preferable emulsifying capacity simultaneously and cause interface polymerization reaction.
3. vinyl chloride according to claim 1 and isoprene in two-phase interface radical polymerization it is characterised in that product
Composition can control simply by the rate of charge of monomer, in copolymer the content of isoprene segment can 10～
Adjust in the range of 42wt.%.
4. boundary radical polymerization according to claim 1 it is characterised in that under room temperature initiated polymerization it is not necessary to
Add other solvents and emulsifying agent, polyreaction efficiency high, meet the requirement of Green Chemistry.
5. a kind of preparation of the vinyl chloride described in claim 1/isoprene copolymer operational approach it is characterised in that step according to
Secondary it is：
1) will be soluble in water for double type surface active initiator, concentration is typically in 2.5～3.0 ‰ scopes, the consumption one of initiator
As be the 2.5～3.0% of vinyl chloride weight, adjust aqueous solution pH value in 4～4.5 scopes, then aqueous solution is placed in airtight
High-pressure reactor in, then be passed through into container nitrogen with exclude inside air；
2) oil-soluble monomer vinyl chloride is injected in reactor, after being sufficiently stirred under room temperature, adds potassium peroxydisulfate saturated solution
(amount of potassium peroxydisulfate is generally and puts into the 1.0～1.5% of monomer weight), post-polymerization occurs within about 5～10 minutes, and very
Fast formation polymer solids dispersion liquid, the polyreaction of first stage typically continues 0.5～1 hour；
3) add second monomer isoprene, the weight ratio of isoprene and vinyl chloride, in 0.1～0.7 scope, has been formed
Polrvinyl chloride by swelling rapidly, after adding second batch potassium peroxydisulfate, polyreaction can proceed with, and continues 1～2 hour,
Finally obtain granular thermoplastic elastomer (TPE).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1474835A (en) * | 2000-11-13 | 2004-02-11 | �������⻯ѧƷ�ع�����˾ | (Co) polymerization of vinyl chloride in presence of stable nitroxyl free radical |
| CN102786608A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Interface free radical emulsion polymerization method |
| CN105884939A (en) * | 2015-06-12 | 2016-08-24 | 宁波大学 | Gemini surface activity initiator and preparation method thereof |
-
2016
- 2016-10-22 CN CN201610938503.2A patent/CN106432649B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1474835A (en) * | 2000-11-13 | 2004-02-11 | �������⻯ѧƷ�ع�����˾ | (Co) polymerization of vinyl chloride in presence of stable nitroxyl free radical |
| CN102786608A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Interface free radical emulsion polymerization method |
| CN105884939A (en) * | 2015-06-12 | 2016-08-24 | 宁波大学 | Gemini surface activity initiator and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZBIGNIEW FLORJANCZYK等: "Polymerization of vinyl chloride in the presence of modified Ziegler-Natta catalysts comprising long chain organoaluminum compounds", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
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