CN106432649B - A kind of environment-friendly preparation method thereof of vinyl chloride/isoprene copolymer - Google Patents
A kind of environment-friendly preparation method thereof of vinyl chloride/isoprene copolymer Download PDFInfo
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- CN106432649B CN106432649B CN201610938503.2A CN201610938503A CN106432649B CN 106432649 B CN106432649 B CN 106432649B CN 201610938503 A CN201610938503 A CN 201610938503A CN 106432649 B CN106432649 B CN 106432649B
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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 present invention relates to a kind of environment-friendly preparation method thereofs of vinyl chloride/isoprene copolymer as thermoplastic elastomer (TPE),It is the copolymer synthetic technology formed based on a kind of water/oil two-phase interface free radical polymerization,Redox reaction occurs with potassium peroxydisulfate at normal temperatures exclusively with a kind of double type surface active initiator,It is repeated several times and generates free radicals and cause vinyl chloride and the independent polymerisation of isoprene at interface,Two kinds of segments are serially connected by initiator molecule,Constitute segmented copolymer,Experiments have shown that when the pH value of aqueous media is in 4~4.5 range,The rate of charge of monomer and the ratio of components of copolymer are very consistent,The content of isoprene segment is adjustable in 10~42wt.% ranges in copolymer,The polymeric reaction condition of this pattern 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 system of vinyl chloride/isoprene copolymer
Preparation Method, the copolymer are a kind of thermoplastic elastomer (TPE)s, its advanced preparation method meets the requirement of Green Chemistry.
Background technology
With the rapid development of modern science and technology and society, people are higher and higher to the performance requirement of high molecular material and day
Become diversification, multifunction, and single polymer is often difficult to meet the needs of people, seems non-to the modification of high molecular material
It is often important.Thermoplastic elastomer (TPE) (TPE) is a kind of elasticity for showing rubber at normal temperatures, and plasticization molding again under high temperature adds
The novel high polymer elastomeric material of work function admirable, it, which has, is not required to vulcanize, is easy to process, at low cost, can be recycled
It is the faster a kind of product of contemporary synthetic rubber field development etc. a series of technology economy advantages.
Polyvinyl chloride (PVC) is a kind of general-purpose plastics, and cheap, yield is big, using wide, and with fire-retardant, resistance to molten
The characteristics such as agent, resistance to ozone, chemical stability be good, have been widely used in national economy every profession and trade.Polyvinyl chloride thermoplastic elastomehc
Property body (PVC-TPE) be elastic material based on PVC, have that compression set is small, high temperature conformality is good, resilience
Greatly, ageing-resistant, oil resistant, bending fatigue strength be high, characteristics, the application such as cheap are increasingly extensive.The existing preparation sides PVC-TPE
Method all biases toward physical means, can be divided into and elastomer blended, introducing crosslinked structure, high relative molecular weight polyvinyl chloride plasticising 3
Kind, vinyl chloride is a lower monomer of polymerization activity, is generally seldom copolymerized with other olefinic monomers, thus greatly limits
The development space of its chemical modification.Water/oil two-phase interface polymerization technique can fundamentally crack this limitation of the technology, make various
The synthesis of olefin copolymer becomes convenient, and meets Green Chemistry requirement.
Realize that the key of interfacial polymerization is to use double type surface active initiator as shown in Figure 1, at the initiator
At the interface of water phase and oil phase, it can be connected in series the polymerisation of water/oil two-phase, this amphiphilic trimethylamine molecule
It can be with water-soluble K2S2O8Redox initiation system is constituted, by repeated Intramolecular electron transfer in nitrogen-atoms
Free radical is formed on adjacent carbon atom, interface free radical can cause the polymerisation of oil phase, can also cause the polymerization of water phase
Reaction, as long as different monomers is added in a certain order, so that it may be polymerize with independent cause, not interfere with each other, because polymerization is anti-
The reactive species answered both are from the same initiator molecule, so what the polymer chain formed was connected together, basic principle
As shown in Fig. 2, it should be noted that, in order to ensure the smooth implementation of copolyreaction, the combination of comonomer must with draw
The pH value of the structure and aqueous media of sending out agent matches.Polyisoprene is a kind of lower polymer elasticity of glass transition temperature
Body can be formed by above-mentioned polymerization methods by the polyvinyl chloride chain of rigidity together with polyisoprene chain link flexible
Thermoplastic elastomer (TPE) can overcome the problems, such as that two kinds of polymer is incompatible completely.
According to 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 K2S2O8It under effect, can generate free radicals, live in no additional surface at normal temperatures
The polymerization for causing hydrophobic vinyl chloride, isoprene in the presence of property agent respectively, obtain other polymerization means be difficult to obtain it is more
Block copolymer, this is a kind of new thermoplastic elastomer of polyvinyl-chloride, and this polymerization methods comply fully with Green Chemistry
Standard --- low energy consumption for normal-temperature reaction, organic solvent-free, without other surfactants.
Invention content
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 characteristics of kind polymerization technique, is generated free radicals under room temperature in specific water/oil two-phase interface, and different alkene lists can be caused
Body realizes separate polymerization, and is concatenated a variety of segments by initiator molecule, forms new copolymer.
Another technical problem to be solved by this invention is to provide double type necessary to above-mentioned interface free radical polymerization
Surface active initiator, the function of its existing surfactant, and redox initiation system can be formed with potassium peroxydisulfate, normal
Temperature is lower to cause various polymerizing olefin monomers.
Another technical problem to be solved by this invention is in the way of above-mentioned interface free radical polymerization and specific
Surface active initiator provides a kind of specific method preparing vinyl chloride/isoprene segmented copolymer.
1, technical solution is used by the present invention solves primary technical problem：A kind of water/oil two-phase interface radical polymerization
Conjunction technology, for basic principle as shown in Fig. 2, it is different from the general polymerisation caused in water phase or oil phase, it is a kind of
Be positioned at the free radical initiation method of two-phase interface, can make water phase, oil phase polymerisation complete independently, and polymeric chain can be made
Section is serially connected on a kind of initiator.
It is beneficial that different monomers can in a manner of homopolymerization respective complete independently, do not interfere with each other, but final obtain
Be more blocks copolymer；
It is beneficial that the composition of copolymer can be controlled simply by the rate of charge of monomer, avoid because of list
The influence that body activity difference forms copolymer；
It is beneficial that the different monomer of each attribute can be formed copolymer by this technology, it is various to synthesize
Copolymer provide extensive feasibility.
2, technical solution is used by the present invention solves another technical problem：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 located in the interface of water/oil two-phase, the energy with emulsive oily monomer
Power, thus no longer need that other emulsifiers are added, after causing polymerization, it just becomes a part for polymer material, no
Emulsifier leakage problem is will produce, will not be had an adverse effect to the performance of polymer material；
It is beneficial that the tertiary amine in initiator can at normal temperatures be reacted with potassium peroxydisulfate, interface free radical is generated, it is double
To aqueous and oiliness monomer polymerization is caused, segmented copolymer is synthesized by multiphase concatenation；
It is beneficial that this initiator can be generated free radicals repeatedly on α-carbon by constantly aoxidizing nitrogen-atoms,
It shows the characteristics of its chain of rings causes, can flexibly control polymerisation, various of monomer is made to be polymerize in a certain order, very
Be conducive to the MOLECULE DESIGN of polyolefin macromolecular material.
3, technical solution is used by the present invention solves another technical problem：Drawn using above-mentioned double type surface-active
Hair agent prepares vinyl chloride/isoprene segmented copolymer specific method, and characterization step is：1) double type surface-active is drawn
It is soluble in water to send out agent, concentration generally in 2.5~3.0 ‰ ranges, the dosage of initiator be usually vinyl chloride weight 2.5~
3.0%, the pH value of aqueous solution is adjusted to faintly acid, ensures the emulsifying capacity of double type surface active initiator, it then will be water-soluble
Liquid is placed in closed high-pressure reactor, then is passed through nitrogen into reactor to exclude internal air；2) by oil-soluble monomer
Vinyl chloride is injected into reactor, and potassium peroxydisulfate saturated solution is added after being sufficiently stirred under room temperature, and (amount of potassium peroxydisulfate is generally
Put into the 1.0~1.5% of monomer weight), about 5~polymerisation generation after ten minutes, and polymer dispersion liquid is quickly formed,
Temperature of reaction system and pressure are risen, but are gradually fallen after rise after supercooling, and the polymerisation of first stage generally continues 0.5
~1 hour；3) weight ratio of second of monomer isoprene of addition, isoprene and vinyl chloride is in 0.1~0.7 range,
The polyvinyl chloride of formation is swollen rapidly, and after second batch potassium peroxydisulfate is added, polymerisation restarts, the diameter of dispersed particle
Become larger, reaction continues 1~2 hour, finally obtains granular thermoplastic elastomer (TPE), the composition of product can pass through the throwing of monomer
Ratio is expected to control.
It is beneficial that since free radical only generates 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 the polymerisation of vinyl chloride carries out at normal temperatures, high pressure not will produce, thus improve
The safety coefficient of operation；
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 advantage of the invention is that：1) the independent equal of various of monomer may be implemented using new interface radical polymerization technique
Coalescence mutually concatenates, and is easy to control the composition and structure of polymer；2) reactivity ratio is avoided, monomer physical difference is copolymerized tradition
The restriction of method is conducive to prepare a greater variety of olefin copolymers, has widened high molecular material development space significantly；3) 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 implementation mode
Present invention is further described in detail with reference to embodiments.
Prepared by vinyl chloride/isoprene copolymer is carried out by following operating procedure：
A. 1.5g double type surface active initiators are dissolved in 500mL water, concentration generally in 2.5~3.0 ‰ ranges, is drawn
The dosage for sending out agent is usually the 2.5~3.0% of vinyl chloride weight, water-soluble to adjust by the way that different amounts of acetic acid or sodium phosphate is added
PH value (pH=9~9.5 of liquid；PH=7~7.5；PH=4~4.5), aqueous solution is placed in closed high-pressure bottle, Xiang Rong
Lead to nitrogen in device to exclude internal air；
B. 55g oil-soluble monomers vinyl chloride (boiling point is -13.4 DEG C) is injected into reactor, after being sufficiently stirred under room temperature
Addition potassium peroxydisulfate saturated solution (amount of potassium peroxydisulfate, which is generally, 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 are risen, and temperature rise is generally not
It more than 10 DEG C, is gradually fallen after rise after supercooling, the polymerisation of first stage generally continues 0.5~1 hour；
C. it is added different amounts of second of monomer isoprene, the weight ratio of isoprene and vinyl chloride is in 0.1~0.7 model
It encloses, the polyvinyl chloride formed is swollen rapidly, and after second batch potassium peroxydisulfate is added, polymerisation restarts, dispersible granule
The diameter of son becomes larger, and reaction continues 1~2 hour, finally obtains granular thermoplastic elastomer (TPE), is done after fully being washed with clear water
It is dry spare.
Product analysis：It is weighed than the consistency with copolymer ratio of components by comparing monomeric charge after polymerisation twice
The actual effect of the initiator is possible to deposit after polymerization to the reaction mixture methanol extraction of unit volume, removing every time
Small molecule monomer, weighed after the obtained washed drying of polymer, just obtain polymer output, polymerization for the first time obtains
The yield M of polyvinyl chloride1, the yield M of copolymer is obtained after second of polymerization1+M2, two kinds thus extrapolated in copolymer are embedding
The quality ratio of components M of section2/M1, and rate of charge m2/m1The mass ratio for two kinds of monomers being added in exactly testing.Acquired experiment
The results are shown in Figure 3.
The control of product composition：Experimental data shows that rate of charge is related with the pH value of polymerisation medium with the relationship of ratio of components,
When pH value is in 4~4.5 range, the relationship of rate of charge and ratio of components substantially on the diagonal, illustrates each polymerisation 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 range2/M1With m2/m1Correlation is bent
Line occurs the cornerwise phenomenon of substantial deviation at pH value 9~9.5 to deviation below diagonal line, illustrates under alkaline condition
The polymerization of isoprene is not very abundant, this may be promoted with the emulsifying capacity of initiator in acid condition, and in alkaline item
The emulsified ability of part declines related.However when pH value is less than 4, the protonation of initiator cause redox reaction by
Resistance, the trigger rate of initiator are substantially reduced, and are unfavorable for the progress of polymerisation, so the pH value of medium is controlled in 4~4.5 models
It encloses proper.
Description of the drawings
The chemical constitution of Fig. 1 double type surface active initiators.
The basic principle of Fig. 2 water/oil two-phase interface free radical polymerization.
The influence that the pH value of Fig. 3 media forms copolymer.
Claims (1)
1. a kind of preparation method of vinyl chloride/isoprene copolymer, it is characterised in that polymerisation uses pair such as lower structure
Subtype surface active initiator：
The preparation method of the vinyl chloride/isoprene copolymer, operating procedure are followed successively by：
1) double type surface active initiator is soluble in water, concentration is controlled in 2.5~3.0 ‰ ranges, double type surface-active
The dosage of initiator is the 2.5~3.0% of vinyl chloride weight, adjusts the pH value of aqueous solution in 4~4.5 ranges, then will be water-soluble
Liquid is placed in closed high-pressure reactor, then is passed through nitrogen into container to exclude internal air；
2) oil-soluble monomer vinyl chloride is injected into reactor, potassium peroxydisulfate saturated solution is added after being sufficiently stirred under room temperature,
The dosage of potassium peroxydisulfate is to put into 1.0~1.5%, 5~polymerisation generation after ten minutes of monomer weight, and quickly form poly-
Object solid dispersion is closed, polymerisation continues 0.5~1 hour；
3) weight ratio of second of monomer isoprene of addition, isoprene and vinyl chloride has been formed in 0.1~0.7 range
Polyvinyl chloride be swollen rapidly, be added second batch potassium peroxydisulfate after, polymerisation can proceed with, and continue 1~2 hour,
Finally obtain granular thermoplastic elastomer (TPE).
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| CN102786608B (en) * | 2012-07-19 | 2014-04-16 | 大连理工大学 | Interface free radical emulsion polymerization method |
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