CN106749796A - Microsuspending method method for producing PVC paste resin - Google Patents
Microsuspending method method for producing PVC paste resin Download PDFInfo
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- CN106749796A CN106749796A CN201611082793.1A CN201611082793A CN106749796A CN 106749796 A CN106749796 A CN 106749796A CN 201611082793 A CN201611082793 A CN 201611082793A CN 106749796 A CN106749796 A CN 106749796A
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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
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
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Abstract
The present invention relates to a kind of production method of PVC paste resin, particularly a kind of microsuspending method method for producing PVC paste resin.Production method, is carried out as follows：Material mix stages, desalted water, emulsifier solution, stearic acid solution, oil-soluble initiator, buffer and VCM are sequentially added into mixing tank successively to be sufficiently stirred for and use homogenizing pump to emulsify, emulsion is added into terminator when polymerization kettle temperature raising polymerization reaches 85~90% conversion ratio, the emulsion after reacted vinyl chloride monomer is reclaimed to be spray-dried, dried material is separated with grader, and the coarse fodder isolated is size-reduced to be mixed to get identical high-quality paste resin with fines that is isolating.Of the invention using above-mentioned technical proposal adds terminator, it is ensured that recovery system is normally run at the end of polymerization compared with prior art, and monomer mass is significantly improved.
Description
Technical field
The present invention relates to a kind of production method of PVC paste resin, particularly a kind of microsuspending method Welvic tree
Fat production method.
Background technology
Vinyl chloride microsuspension polymerization PVC paste resin is developed on the basis of emulsion polymerization of VC, and this is a kind of newer
Method, has industrialized early in middle 1960s.Its flow is：First by VCM, desalted water, emulsifying agent mechanical homogenization
Method is made the emulsus of stabilization（Particle diameter is at 1.0 μm or so）, then it is polymerized（Oil-soluble initiator must be selected）.The life
Production. art need to pay special attention to following influence factor：From suitable compound emulsifying agent and particle modifying agent system；Condensate
It is the homogenizing of component；Mixing speed；Water is appropriate with the ratio between monomer.The moderate in grain size of the PVC paste resin for producing in this way, stream
Dynamic property is excellent, and emulsifier is few, and the heat endurance and water-resistance of resin are improved.
Traditional vinyl chloride microsuspension polymerization is divided into chemicals and prepares, is polymerized, reclaim blowing, spray drying point, crush, sieve
Point and sewage is continuous several operations such as automatically processes.
Chemicals is prepared：It is to be fed after processing aid, emulsifying agent, stearic acid etc. are configured with hot water etc., it is pure during charging
Water, initiator etc. are added in tank diameter simultaneously, the chemicals after configuration well is added successively and adds VCM again, in dispersion pump after adding
In the presence of be circulated in tank diameter, make material dispersion turn into stabilization fine droplet.According to the flow worked out, turn trough enters again after
To in polymeric kettle.
Polymerization：After being dispersed through the scattered feed liquid of pump and fully entering polymeric kettle, polymeric kettle starts to warm up polymerization, due to polymerization
It is exothermic reaction to react, it is necessary in time remove reaction heat.Thus it is guaranteed that the supply of jacketed low-temperature water is to maintain polymerization normal anti-
The key answered.When reaction temperature is constant, and pressure is reduced to setting, proved response terminates, and starts to open at polymeric kettle top monomer
Recovery valve carries out the recovery of VCM.
Reclaim blowing：Carry out first from receipts are pushed back, while making latex temperature in kettle reach one to steam is passed directly into kettle
Definite value, when pressure reaches 0.05mpa in kettle（Table）, the Coarse Aggregate wet-milling that slurry in kettle is carried secretly latex by Shi Shi disintegrating machines,
Then squeezed into by screw pump and dry groove（Negative pressure discharges）.Polymeric kettle is vacuumized after blowing is complete, proceeds to force back
Receive, steam blowing, vinyl chloride in thorough cleared kettle, opening kettle cover carries out high-pressure wash, is sprayed after having cleaned and pipeline is clear
Wash.After covering kettle cover, polymeric kettle is vacuumized and steam blowing, removing in kettle air and carries out leak test inspection, uses vinyl chloride list
Body vacuum breaker, vacuumize again, pressure reaches 0.05mpa in chlorination vinyl monomer to kettle（Table）, anti-stick kettle agent spray is carried out to polymeric kettle
Apply, the complete rear next kettle charging of wait.
Spray drying and crushing：The latex dried in groove is pumped into spray dryer by wet type disintegrating machine and screw rod,
Bag hose, size-reduced machine crushing again that dried resin enters with air-flow, screening, malleation are delivered to finished product bin, packaged
Shaping feeding warehouse for finished product after machine packaging.Waste gas is emptied after being filtered through bag hose.
Sewage disposal：Polymeric kettle and equipment flushing water are collected in wastewater disposal basin and squeeze into automatic empty vapour pressurization after mixing slow mixing soon again
Floater remover is included except the sludge of concentration, and sludge is pumped after centrifuge dewatering collects into mud cake packaging after concentrating again and resaled, to remove
EPVC slags, mother liquor pumping proceeds next step treatment toward wastewater disposal basin in three phase device areas.
Traditional production technology, polymerization formula and equipment exist substantially not enough, and the problem for reflecting has：Resin paste viscosity is inclined
It is high, gel time is long, product mechanical strength is not high, heat endurance is poor；Recovery system blocking is serious, it is poor to reclaim monomer mass,
It is back to after suspension polymerisation that to be also easy to produce coarse fodder, product flake more；Primary particle is mixed with offspring after drying and crushing,
Reduce the quality scale of resin.
The viscosity of so-called PVC paste resin is that the fine particle for instigating PVC is suspended in liquid plasticizer, and the liquid for being formed
The viscosity of mixture.This liquefied mixture is a kind of non-uniform dispersion of macromolecule, wherein also include colorant, stabilizer,
Viscosity depressant, filler etc..Its range of viscosities can be from coming down in torrents property liquid, so that the thickener of stiff.According to different purposes and
Different technological method for processing, also have different requirements to the viscosity of PVC paste.Heated it is changed into this liquefied mixture is last
Solid, this process turns into gel.There is document report achievement in research in this respect.Kingdom weighs, and the PVC paste resin such as power gathers
Influence right and that paste viscosity is to gelatinization performance《Polyvinyl chloride》1990,2 phases, 8-11 pages.Proposed in text, be not agglomerated into two
The discrete easy gel of primary particle of secondary particle, the PVC paste resin easy gel of the PVC paste resin than HMW of low-molecular-weight.
The measure of the reduction PVC paste resin viscosity such as Huanghai Sea great waves, Qiu Ying《Polyvinyl chloride》2007,12 phases, 12-13 pages then proposes paste
The relatively low 140-150 DEG C of paste viscosity of resin spray drying inlet temperature is relatively low, and 58 DEG C of rate of change in viscosities of outlet temperature are minimum.Also propose
The small adhesion plasticizer of paste resin particle diameter bigger serface pastes viscosity reduction less and resin size skewness is advantageously reduced and pastes viscous
Degree.
Therefrom it can be seen that in drying process primary particle can be caused to gather into offspring, and this agglomerated thing need to be in powder
The disintegration of broken process is primary particle, although may recover the particle diameter of primary particle, but be can not show a candle in processing characteristics without coalescence-broken
Broken primary particle, the big particle diameter distribution of particle diameter is wide to be conducive to processing and improving performance.As long as therefore selecting point sample of certain particle diameter
Sieve sub-sieve as much as possible goes out primary particle, and without all being crushed, particle is meticulous unfavorable to processing on the contrary.Point
The resin that goes out of level makes particle diameter distribution broaden to be similar to the resin property that seeded emulsion polymerization is obtained with the mixed with resin after crushing.
The method that CN103920643B describes grading in PVC paste resin production, can separate primary particle
Go out, but be not directed to improve the otherwise performance of primary particle, and only 80% or so particle is not size-reduced, its
Remaining 20% resin it is size-reduced for other aspect.The method for being not directed to reduce offspring.Homogenous quantities paste resin yield is not high.
The content of the invention
The purpose of the present invention is overcoming the deficiency of prior art so as to provide a kind of reducing energy consumption, improve paste resin quality
Microsuspending method method for producing PVC paste resin.
The present invention is adopted the following technical scheme that：
A kind of microsuspending method method for producing PVC paste resin, is carried out as follows：Material mix stages, by desalted water,
It is abundant that emulsifier solution, stearic acid solution, oil-soluble initiator, buffer and VCM are sequentially added into mixing tank successively
Homogenizing pump emulsification is stirred and used, emulsion is added into terminator when polymerization kettle temperature raising polymerization reaches 85~90% conversion ratio, returned
Receive the emulsion after reacted vinyl chloride monomer to be spray-dried, dried material is separated with grader, and that isolates is thick
Material is size-reduced to be mixed to get identical high-quality paste resin with fines that is isolating.
Using above-mentioned technical proposal the present invention compared with prior art, terminator is added at the end of polymerization, it is ensured that
Recovery system is normally run, and monomer mass is significantly improved.
Preferred scheme of the invention is：
Buffer is that diammonium hydrogen phosphate and ammonium phosphate are multiplexed, and the mass ratio of the two is 1：2~2：1.
The addition of buffer is the 0.005-0.05w/% of vinyl chloride addition.
Terminator is diethyl hydroxylamine and BHT（2,6- di-t-butyl 4- hydroxy-methylbenzenes）The two mixing.
Terminator consumption is the 0.002w/%-0.02w/% of vinyl chloride addition.
The preparation method of terminator is：Both BHT and diethyl hydroxylamine are respectively placed in respective solvent, then with emulsification
Agent is configured to the emulsion of stabilization.
BHT is dissolved in epoxidized soybean oil, diethyl hydroxylamine is dissolved in after forming diethyl hydroxylamine solution in desalted water, then will
Diethyl hydroxylamine solution is thoroughly mixed to form emulsion with emulsifier tween 80, BHT solution, and BHT is 50~150 matter in emulsion
Amount part, the mass parts of diethyl hydroxylamine 150~50, the mass parts of epoxidized soybean oil 300~600, Tween 80 are 7~20 mass parts, take off
Salt solution is 300~500 mass parts.
Grader uses turbine gas streaming grader.
Brief description of the drawings
Fig. 1 is production technology paste resin grain size curve of the present invention.
Fig. 2 is traditional（Prior art）Technique pastes resin grain size curve.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment describe in detail the present invention：
Embodiment 1：
The mechanical strength of product has outside the Pass except the species and addition with additive, processing conditions, is heavily dependent on
Molecular weight and molecualr weight distribution, if in the case of mean molecule quantity identical, the molecular weight of PVC paste resin gets over concentration, product
Intensity it is higher.Existing process, the polymerisation of conversion rate of vinyl chloride 90% or so terminates, and is then carried out at a temperature of 70~80 DEG C
Unreacted monomer is reclaimed, and remaining initiator continues to produce the free radical carries out polymerisation with monomer in system, due to temperature compared with
What height was generated is the polyvinyl chloride of low-molecular-weight, and mean molecule quantity is reduced to a certain extent, and molecular weight distribution substantially broadens, such as
Fruit will make mean molecule quantity keep the constant ratio that certainly will increase HMW PVC, can undoubtedly improve gel difficulty.Monomer is returned
A part of free radical of receipts process and initiator can enter recovery system with together with reclaiming monomer, bring unfavorable to subsequent treatment.
Another part initiator enters spray drying in remaining in paste resin latex.At 140~160 DEG C, decomposition of initiator come from by
Base, free radical attack PVC macromoleculars form macromolecular radical, and two or more macromolecular radicals react, and produce friendship
Connection, winding-type offspring are quite big on processing influence even across the broken performance also recovered less than primary particle.
The present embodiment reduces small-molecular-weight PVC and produces crosslinking, the method for winding-type offspring to be added at the end of polymerization
Terminator.Also a kind of offspring is the agglomeration due to being produced between drying process resin particle, is a kind of physical process, is passed through
Form and property broken and that easily return to primary particle.
PVC paste resin heat endurance is poor, causes it to be ground through nuclear magnetic resonance in process problem easy to change of being heated
Study carefully the problem for being the discovery that resin internal structural defects.Using 1H spectrums and 13C spectrum nuclear magnetic resonance method research PVC macromolecule internal structures
Influence to heat endurance, if PVC macromolecule internals are more than or equal to 0.20mol/%, three-level charcoal containing double bond（One carbon atom is same
Shi Yusan carbon atom is connected）Structure is more than or equal to 0.35mol/% or the two summation is more than or equal to 0.50mol/%, the heat of resin
Stability is seriously deteriorated.
Research finds that the Determining Micro Acid produced containing Determining Micro Acid or polymerisation in raw material vinyl chloride is polyvinyl chloride macromolecular
The catalyst of dehydrochlorination, system PH is lower, and dehydrochlorination reaction is stronger.In just being produced after macromolecular PVC removing hydrogen chloride
Portion's double bond, and macromolecular PVC internal double bonds are allylic structures, are easier to make for the reaction of removing hydrogen chloride.In processing
The degradation reaction of thermal histories dehydrochlorination is serious, and heat endurance is poor.
The present embodiment, it is internal double that discovery adds a small amount of buffer substantially to ensure in raw material mix stages in system
Linkage content is in below 0.10mol/%.The species of buffer it is many as sodium acid carbonates, ammonium hydrogen carbonate, calcium phosphate, sodium dihydrogen phosphate,
Disodium hydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate etc., buffer can be used alone can also compound use, its consumption be chloroethene
0.005~0.05w/% of alkene addition, preferably 0.01~0.02w/%.The present embodiment is multiple using diammonium hydrogen phosphate and ammonium phosphate
With the ratio of the two is 1：2~2:1, the addition of buffer can also strengthen the stability of emulsion, prevent " toilet cream "
The product of formula.Adding buffer can also reduce the consumption about 10% of emulsifying agent.
Polymerization later stage conversion rate of vinyl chloride 85~90%, the VCM that can move freely is little.Initiator is relatively
Many, the carbon atom on free radical attack PVC macromolecular chains that decomposition of initiator goes out generates macromolecular radical, then macromolecular
Free radical reacts to form side chain with VCM again, that is, tertiary carbon origin.The monomer that the polymerization later stage moves freely is got over
Less, the tertiary carbon of reaction temperature generation higher is also more.Chlorine atom on same tertiary carbon also easily with adjacent carbon atom on
There is removing hcl reaction in hydrogen atom, generate PVC macromolecule internal double bonds.Be cause polyvinyl chloride resin heat endurance difference it is another
Reason.
When polymerisation reaches the conversion ratio of regulation, terminator is added reaction is stopped completely.Avoid excessive generation
PVC macromoleculars containing tertiary carbon.Can be used as the terminator including but not limited to acetone contracting of microsuspending method polyvinyl chloride resin production
Thiosemicarbazides, AMS, diethyl hydroxylamine, NO, sodium sulfite, bisphenol-A and various hindered phenolics such as BHT（2,6- bis-
Tert-butyl group 4- hydroxy-methylbenzenes）Deng；Selection terminator should be in line with the principle that nontoxic, cost performance is high, effect is good.The consumption of terminator is
0.002w/%~the 0.02w/% of vinyl chloride addition, normal usage 0.006w/%~0.015w/%.Terminator can be configured to water
Solution is added, it is also possible to be configured to organic solution or emulsion is added.
Terminator used by the present embodiment be nontoxic diethyl hydroxylamine and can be used for food, medicine equipment can cosmetics nothing
Malicious Wei Zu Fen BHT, are that BHT epoxidised soybean oils, emulsifying agent, deoxygenated water and diethyl hydroxylamine are made into emulsion to add polymerization
Kettle, BHT is 50~150 mass parts, the mass parts of epoxidized soybean oil 300~600, Tween 80 in emulsion（Polyoxyethylene mountain
Pears alcohol monoleate.Trade name known to whole world professional, from English Tween transliteration）It is 7~20 mass parts, two
The mass parts of ethylhydroxyl amine 150~50, desalted water are 300~500 mass parts.Can ensure that three-level charcoal contains in PVC macromoleculars completely
Amount is in below 0.15mol/%.Adding terminator can also reduce small-molecular-weight PVC and produce crosslinking, winding-type offspring, significantly
Improve product quality.Adding terminator is greatly lowered free radical and initiator content in recovery VCM, it is ensured that
Recovery system is normally run, and monomer mass is significantly improved.
It is necessary why domestic and international microsuspending method chloroethylene polymerization is all not added with buffer and terminator for explanation.First from chloroethene
Alkene emulsion polymerization is talked about.Emulsion polymerization requires that very strictly VCM, water, water soluble, redox initiator and emulsifying agent exist to stirring
It is uniformly dispersed under stirring action, forms VCM droplet, also referred to as micella.Be there is also about in water phase beyond 1% micella
Free VCM, vinyl chloride, free vinyl chloride and gas phase vinyl chloride three in micella under uniform temperature, pressure are put down
Weighing apparatus.Emulsifying agent is centered around droplet surface, and the lipophilic group of emulsifying agent points to monomer, and hydrophilic radical is contacted with water.Usually used
Initiator is water soluble persulfates and reducing agent sodium hydrogensulfite, and initiation is carried out in water phase, with redox
As a example by initiation system, in polymeric reaction temperature scope
（40~60 DEG C）S2O8= + HSO3- → SO4= + SO4-° + HSO3-°（1）
Generation SO4- ° and HSO3- ° two free radicals.Vinyl chloride in free radical initiation micella carries out polymerisation, with anti-
The carrying out answered, monomer is gradually decreased in micella, destroys original balance, and the Free Monomer in water phase is to generation polymerisation
Spread in micella, monomer enters water mutually as Free Monomer in there is no the micella of polymerisation, in generation polymerisation micella
Vinyl chloride, the micella that do not react in vinyl chloride, free vinyl chloride and gas phase vinyl chloride reach new balance.With
The continuous of reaction is carried out, and the vinyl chloride in the micella that do not react is gradually decreased to a certain extent, ultimately results in micella disappearance.And
The micella for reacting ultimately forms latex, and generally, the latex particle size that emulsion polymerization is obtained is less than 0.2 μm.But by
In the large usage quantity of emulsifying agent（The 4~5% of monomer weight）, emulsifying agent is lauryl sodium sulfate or neopelex,
Strong base weak acid salt is, also there is certain antacid ability.Sometimes containing acid in monomer, dehydrochlorination is produced in course of reaction
Acid is neutralized by losing a part of emulsifying agent, and such as tartaric acid content is excessive, destroys the emulsifying capacity of emulsifying agent, also occurs sometimes
Coarse grain footpath and the situation of " toilet cream ".
The latex of generation reclaims unreacted VCM by degassing, eventually passes spray drying and obtains finished product paste tree
Fat.Because degassing temperature is at 75 DEG C or so, spray drying temperature at 140~160 DEG C, and redox system 60 DEG C with
It is upper that following reaction will occur：
S2O8= + HSO3- + H2O → 3HSO4 - (2)
Free radical is not produced, therefore does not consider the influence that residual initiators bring, also just do not add necessity of terminator.
Vinyl chloride microsuspension polymerization PVC paste resin is developed on the basis of emulsion polymerization of VC, and this is a kind of newer
Method, has industrialized early in middle 1960s.Except emulsifier is few（Only the 1.5~2.0% of monomer consumption）、
With homogenizing pump, further emulsification is outer using oil-soluble initiator and mixed emulsion for initiator, with emulsion polymerization very close to, because
This, has also continued the custom for being not added with buffer and terminator.Latex after removing unreacted monomer is dried into groove is dried
Latex in groove is pumped into spray dryer by wet type lump breaker and screw rod, and dried resin enters with air-flow
One bag hose, by entering collection powder groove after vibratory sieve screening, the material in collection powder groove enters grader, and resin after classification enters mixed
Hopper.Vibration oversize is mixed into pulverizer crushing with the coarse fodder that grader is separated, and screening, malleation are delivered to mixing tank for coating colors, mix
Uniform rear feeding finished product bin is closed, shaping feeding warehouse for finished product after packaged machine packaging.Waste gas is emptied after being filtered through bag hose.
In the present embodiment, the PVC paste production of resins process powder grading method uses turbine airflow classification
Machine.Machine air-flow sends into PVC paste resin powder, and turbine classifier is mainly according to the particle of different resins particle size,
The centrifugal force that is subject in rotary pneumatic flow field principle of different sizes is classified.The air stream for mixing material is introduced into classification
Machine bottom, the classification chamber that an air-flow for free volute enters grader is formed through water conservancy diversion, and classification has a horizontal positioned in chamber
Grading wheel rotor, by the rotation of grading wheel rotor, produce a rotary pneumatic flow field；The hollow parts of rotating shaft simultaneously are by air draft
Machine causes a negative pressure, the air that carry material is entered grading wheel along classifier rotor edge, in the shape of a spiral in turbine
The heart is moved.Thick particle is thrown out of grading wheel more than air-flow due to the centrifugal force suffered by it to the viscosity resistance that it is produced, through two
Exported by meal after secondary wind cleaning and discharged；And fine grained is sucked into rotor center with air together, cylinder is drawn by fine powder and is discharged to thing
Material collector is collected.So as to realize the classification of different-grain diameter particle.Inlet amount and air capacity can according to demand be adjusted.By adjusting
The rotating speed for saving grader turbine rotor realizes 5~50 μm of different grades of paste fractionation of resins.
The present embodiment, adds terminator at the end of polymerization, reduces in drying process, be crosslinked a PVC generation,
Winding-type offspring, therefore greatly reduce the coarse grained amount of offspring, grader can make 85~95%, generally 90% with
On resin be not required to through crushing.The offspring coarse fodder being classified out（Less than or equal to 10%）Due to being drying process resin particle
Between the agglomeration that produces, be a kind of physical process, by crushing and easily returning to the form and property of primary particle, classification is gone out
Resin with crush after mixed with resin particle diameter distribution is broadened, be similar to the bimodal particle size of the resin that seeded emulsion polymerization is obtained
Preferably, processing characteristics is excellent for the parameters such as distribution and performance, material circularity, is bordering on 100% identical high-quality paste resin yield.Crush
Board number reduces 80%, and various consumption are greatly lowered, remarkable in economical benefits.
As a example by producing glove material.Desalted water 19.5t, ABVN 3.0kg, peroxy dicarbonate diethoxy second
Ester（EEP) 3.0kg, lauryl sodium sulfate 285kg, hexadecanol 210kg, diammonium hydrogen phosphate 2kg, ammonium phosphate 1kg and vinyl chloride
Monomer 19t, adds in dispersion slot under agitation, is sufficiently stirred for, and is then further emulsified with homogenizing pump.Emulsion is sent into
48m3Polymeric kettle, is warmed up to 43 DEG C and starts polymerization, after pressure declines 0.2mpa in kettle, adds terminator emulsion 20kg
（BHT, diethyl hydroxylamine, epoxidized soybean oil, Tween 80, desalination water content be respectively 10w/%, 10w/%, 35w/%, 1.0w/% and
44w/%）, reacted vinyl chloride MONOMER RECOVERY is then carried out in kettle, while steam is passed through to kettle chuck, with 1 DEG C/minute of speed
Emulsion temperature in kettle is set to be raised to 75 DEG C, until pressure drop 0.05mpa in kettle（Table）, kettle internal emulsification liquid is leaked into spray drying and is received
Groove.The spray-dried device of latex is dried under the conditions of 155 DEG C of inlet temperature, 58 DEG C of outlet temperature, dried material classification
Machine is separated, and the coarse fodder isolated is size-reduced to be mixed with fines that is isolating, obtains product.53 μm of finished product grain size, average degree of polymerization
1648, Mw/Mn=2.3342, apparent viscosity 1890mpa.S, gel time 94 seconds, heat-stable time 6 point 17 seconds.
The bimodal particle size distribution that resin is pasted similar to the seed law is shown in Fig. 1, particle diameter distribution is wide.Control present invention side
The paste molecular resin amount distribution of method production is concentrated, gel time is short, and heat endurance is good, be advantageous for the high-quality paste tree of processing
Fat.
Embodiment two：
It is also as a example by producing gloves：Feeding quantity and operating condition are identical with example one, except lauryl sodium sulfate addition
It is 256.5kg.Dried material is separated with grader, and the coarse fodder isolated is size-reduced to be mixed with fines that is isolating, is obtained
Product.54 μm of finished product grain size, average degree of polymerization 1650, Mw/Mn=2.3282, apparent viscosity 1885mpa.S, gel time 94 seconds,
Heat-stable time 6 point 20 seconds.
Embodiment three：
Desalted water 19.5t, ABVN 3.0kg, peroxy dicarbonate diethoxy ethyl ester（EEP) 3.0kg, dodecyl
Sodium sulphate 285kg, hexadecanol 210kg and VCM 19t are added in dispersion slot under agitation, are sufficiently stirred for, then
Further emulsified with homogenizing pump.Emulsion sends into 48m3Polymeric kettle, is warmed up to 43 DEG C and starts polymerization, when pressure declines in kettle
After 0.2mpa, reacted vinyl chloride MONOMER RECOVERY is carried out in kettle, while being passed through steam to kettle chuck, the speed with 1 DEG C/minute makes
Emulsion temperature is raised to 75 DEG C in kettle, until pressure is down to 0.05mpa in kettle（Table）, kettle internal emulsification liquid is leaked into spray drying and is received
Groove.Latex is pumped into spray dryer by wet type disintegrating machine and screw rod, and spray-dried device is in 155 DEG C of inlet temperature, outlet
Dried under the conditions of 58 DEG C of temperature, bag hose, size-reduced machine crushing again that dried resin enters with air-flow, screening, malleation are defeated
Deliver to finished product bin and obtain product.46 μm of finished product grain size, average degree of polymerization 1576, Mw/Mn=2.7524, apparent viscosity
2690mpa.S, gel time 187 seconds, heat-stable time 4 point 35 seconds.
Example IV：
Feeding quantity and operating condition are identical with example IV example, except lauryl sodium sulfate addition is 256.5kg.After drying
Resin enter with air-flow bag hose, again size-reduced machine crush, screening, malleation are delivered to finished product bin and obtain product.Finished product
64 μm of particle diameter, average degree of polymerization 1582, Mw/Mn=2.7494, apparent viscosity 2750mpa.S, gel time 196 seconds, when thermally-stabilised
Between 4 points 47 seconds.
From above example one and embodiment two, due to adding proper amount of buffer, the amount of emulsifying agent is reduced
10%, the product quality of resin is substantially unaffected.
10% is reduced by the visible amount due to not adding buffer, emulsifying agent of embodiment three and example IV, the particle diameter of resin is bright
It is aobvious thicker.
Claims (8)
1. a kind of microsuspending method method for producing PVC paste resin, is carried out as follows：Material mix stages, by desalination
Water, emulsifier solution, stearic acid solution, oil-soluble initiator, buffer and VCM are sequentially added into mixing tank successively
Homogenizing pump emulsification is sufficiently stirred for and used, emulsion is added when polymerization kettle temperature raising polymerization reaches 85~90% conversion ratio and is terminated
Agent, reclaims the emulsion after reacted vinyl chloride monomer and is spray-dried, and dried material is separated with grader, is isolated
Coarse fodder size-reduced identical high-quality paste resin is mixed to get with fines that is isolating.
2. microsuspending method method for producing PVC paste resin according to claim 1, it is characterised in that：Buffer is phosphorus
The ammonium of sour hydrogen two and ammonium phosphate are multiplexed, and the mass ratio of the two is 1：2~2：1.
3. microsuspending method method for producing PVC paste resin according to claim 1, it is characterised in that：Buffer plus
Enter the 0.005-0.05w/% that amount is vinyl chloride addition.
4. microsuspending method method for producing PVC paste resin according to claim 1, it is characterised in that：Terminator is two
Ethylhydroxyl amine and BHT（2,6- di-t-butyl 4- hydroxy-methylbenzenes）The two mixing.
5. the microsuspending method method for producing PVC paste resin according to claim 1 or 4, it is characterised in that：Terminator
Consumption is the 0.002w/%-0.02w/% of vinyl chloride addition.
6. microsuspending method method for producing PVC paste resin according to claim 4, it is characterised in that：The system of terminator
Preparation Method is：Both BHT and diethyl hydroxylamine are respectively placed in respective solvent, then the emulsification of stabilization is configured to emulsifying agent
Liquid.
7. microsuspending method method for producing PVC paste resin according to claim 6, it is characterised in that：BHT is dissolved in
In epoxidized soybean oil, diethyl hydroxylamine is dissolved in after forming diethyl hydroxylamine solution in desalted water, then by diethyl hydroxylamine solution with
Emulsifier tween 80, BHT solution are thoroughly mixed to form emulsion, and BHT is 50~150 mass parts, diethyl hydroxylamine in emulsion
150~50 mass parts, the mass parts of epoxidized soybean oil 300~600, Tween 80 are 7~20 mass parts, desalted water is 300~500 matter
Amount part.
8. microsuspending method method for producing PVC paste resin according to claim 1, it is characterised in that：Grader is used
Turbine gas streaming grader.
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| CN109575165A (en) * | 2018-12-20 | 2019-04-05 | 青岛海湾化学有限公司 | A kind of ethylene process polyvinyl chloride polymerization system and its control method |
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