CN105884945B - The method for improving micro suspension PVC paste resin production efficiency - Google Patents
The method for improving micro suspension PVC paste resin production efficiency Download PDFInfo
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- CN105884945B CN105884945B CN201610492338.2A CN201610492338A CN105884945B CN 105884945 B CN105884945 B CN 105884945B CN 201610492338 A CN201610492338 A CN 201610492338A CN 105884945 B CN105884945 B CN 105884945B
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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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Abstract
The present invention relates to a kind of production method of PVC paste resin, particularly a kind of method for improving micro suspension PVC paste resin production efficiency.It carries out as follows：Polymeric kettle will be added in after initiator, emulsifier, assistant for emulsifying agent, vinyl chloride monomer and desalination water emulsification, reacted at 40 DEG C~60 DEG C, reaction starts 30 to after sixty minutes, adds vinyl chloride monomer.Compared with prior art, the present invention with the viscous kettle degree of mitigation, production efficiency, reduction auxiliary agent consumption are improved, and particle diameter and particle diameter distribution can pass through intermediate the advantages of adding in amount of monomer and adding in speed control.Solve the problems, such as that the matter homogenizing time is longer in current PVC paste resin production, so that material particular diameter not only meets process requirements but also still ensures that emulsion droplets stable and product cut size and particle diameter distribution in suitable scope after vinyl chloride monomer is added after homogenizing, homogenising time is shortened, improves production efficiency.
Description
Technical field
The present invention relates to a kind of production method of PVC paste resin, particularly a kind of raising micro suspension Welvic
The method of production of resins efficiency.
Background technology
Polyvinyl chloride（PVC）It is that such resin is mainly applied so that paste forms are made as its name suggests to paste resin, Ren Menchang
It is referred to as plasticized paste with such paste, is a kind of unique liquid form of the igelite under rough.Paste resin often by
Lotion and microsuspending method are made.
For PVC paste resin because granularity is fine, quality has nonflowing character as talcum powder.PVC paste resin is same
Stable suspension is agitated to form after plasticizer mixing, that is, PVC paste material is made or makees PVC plasticized pastes, PVC colloidal sols, and
People are exactly used for being processed into end article in this form.During paste producing, according to different product needs, addition is various
Filler, diluent, heat stabilizer, foaming agent and light stabilizer etc..
The development of PVC paste Resin Industry provides a kind of only heated new liquid for just becoming polrvinyl chloride product
Material.This kind of liquid material configuration is convenient, and performance is stable, easy to control, easy to use, product properties is excellent, chemical stability is good,
With certain mechanical strength, easy coloring etc., thus be widely used in artificial leather, flooring laminate, the production of medical, precision instrument and
Elastomeric glove, vinyl toy, soft trade mark, wallpaper, the leaching modeling industry of catering trade（Electronic handle medical instrument, labour protection hand
Set etc.）, paint, foamed plastic, conveyer belt, the production of automobile decoration etc..
Compared with traditional suspending resin, PVC paste resin has the following advantages：
（1）Process equipment is inexpensive；（2）Mold simple cheap；（3）It can be made into F-SP；（4）Foaming is easy；（5）Product
Heated number is few, and can on a small quantity, multi items are produced.
Global paste PVC resin industry is developed always with fast speed, and particularly nearly ten years, production capacity is with yield in jump
Formula increases, and increases in Asia especially pronounced.2014, about 5,500,000 tons/year of whole world paste polyvinyl chloride resin aggregated capacity, Chinese production capacity
About 710,000 tons, account for global aggregated capacity 13%.
Preparation method mainly has：
1st, emulsion method
Emulsion polymerization formula mainly has VCM, water, water soluble starter and emulsifier.Emulsion polymerization is very tight to stirring requirement
Lattice, initiation carry out in water phase, and usually used initiator is the oxidation of water soluble persulfates and sulphite
Also original system, reaction speed are related with the addition speed and amount of reducing agent.Under normal circumstances, the latex particle size that emulsion polymerization obtains
Less than 0.2 μm, in order to achieve the purpose that increase latex particle size, lotion seeded polymerization is developed, latex particle size is made to increase to 1.0
μm or so.In emulsion polymerization, if there is generated high polymer latex exists, control material proportioning and condition, in principle
VCM only polymerize on generated latex particle, without re-forming new particle；This generated high polymer latex just looks like
Crystal seed, because being referred to herein as " lotion seeding polymerization.Not only there is rational grain size, it is necessary to there is appropriate particle diameter distribution, could obtain
To the PVC paste resin of function admirable.Emulsifier is critically important in emulsion polymerization, and quantity used determines the population of initiator, and
Main function has been risen to the size of final latex particle.Especially when carrying out seed generation, using high trigger rate and low dense
Degree emulsifier is produced, and present latex particulate Size Distribution can be made to narrow.
2nd, microsuspending method
Microsuspension polymerization is that a kind of newer method of PVC paste resin is made, and flow is：First VCM, oil-soluble are triggered
Stable emulsus is made of the method for mechanical homogenization for agent, emulsifier and water（Grain size is at 1.0 μm or so）, then it is polymerize.With
The excellent flowability of the PVC paste resin of this method production, emulsifier is few, and the thermal stability and water-resistance of resin obtain
Improve.The production technology need to pay special attention to following influence factor：Select suitable compound emulsifying agent and particle modifying agent
System；The homogenizing of polymerization system component；Mixing speed；The ratio between water and monomer are appropriate.It is to make the most extensively in current world wide
Method.Also it will not go into details herein for some modification methods such as mixing method etc..
Traditional vinyl chloride microsuspension polymerization be divided into chemicals prepare, polymerization, recycling blowing, spray drying classification, crush,
Sewage such as continuously automatically processes at several processes.
Chemicals is prepared：It is to be fed after the auxiliary agents such as emulsifier, assistant for emulsifying agent are configured with hot water etc., pure water during charging,
Initiator, while add in tank diameter, the chemicals added successively after configuration well adds VCM disperseing the effect of pump after adding again
Under be circulated in tank diameter, material dispersion is made to become stable fine droplet.According to the flow of establishment, turn trough enters to polymerization again after
In 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 polymerizeing
It reacts for exothermic reaction, 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.Work as pressure rise, proved response terminates when reaction temperature reduces, and starts to be discharged to when pressure is down to 4Kg/cm2
Blowpit is carried out at the same time the recycling of vinyl chloride monomer.
Recycle blowing：It is carried out first from receipts are pushed back, when pressure reaches 0.05mpa in kettle（Table）, after blowing is complete to polymeric kettle into
Row vacuumizes, and continues to force recycling, steam blowing, thoroughly vinyl chloride in cleared kettle, opens kettle cover and carry out high-pressure wash, clearly
It is sprayed after washing and pipeline cleaning.After covering kettle cover, polymeric kettle is vacuumized and steam blowing, remove air in kettle and go forward side by side
Row leak test inspection with vinyl chloride monomer vacuum breaker, vacuumizes again, and pressure reaches 0.05mpa in chlorination vinyl monomer to kettle（Table）, it is right
Polymeric kettle carries out anti-stick kettle agent spraying, and next kettle charging is waited after complete.
There are many deficiencies for traditional technique so that plant capacity is low, and product quality is bad, and cost remains high.
It is homogenizing first.PVC paste resin particle size difference is to the apparent density of resin, mobility, transport, packaging and answers
With all having a significant impact.Therefore it must assure that the grain size of PVC paste resin within the specific limits and to be evenly distributed.PVC paste tree
The grain size of fat is largely determined by the size of vinyl chloride drop.General microsuspending method chloroethylene polymerization, monomer will be dispersed into
0.1-2.0 μm of drop, and keep stablizing in entire polymerization process.Except selecting suitable emulsifier and assistant for emulsifying agent,
Homogenizing is crucial.Usual vinyl chloride microsuspension polymerization homogenization process be by VCM monomers, deionized water, emulsifier and assistant for emulsifying agent,
Initiator and other auxiliary agents etc. are disposably added in premix slot, and being sufficiently stirred premixes material.Then after making premix with homogenizer
Material under fierce mechanical shear stress effect, be emulsified into the lotion of appropriate particle size.General continuous Xun Huan is after 30 minutes, and 2/3
Lotion continue cycling through, 1/3 lotion is continuously into kettle.Emulsification times are long, low production efficiency.So add in the lotion one in kettle
It point only emulsifies 1 time, some emulsification 2 times, 3 times ... n times, the grain size of drop and the grain size of final resin are uneven in lotion
It is even, influence use and the processing performance of product；
The factor of another influence production efficiency and product quality is exactly that the space of reaction kettle cannot sufficiently utilize.By
There are larger density contrast between vinyl chloride monomer and Corvic, with the continuous progress of polymerisation, polymeric kettle
Interior volume of material appearance is significantly shunk, and the heat transfer area of reaction kettle is reduced, and is moved thermal energy power and is declined, production capacity reduces；Due to volume
It shrinks, increases gas-phase space in kettle, viscous kettle most easily occurs for gas-liquid interface, and kettle pasting matter declines the quality of product.In order to overcome
This point have document propose " phase adds a certain amount of vinyl chloride monomer after polymerisation, make full use of initiator remaining in kettle into
Single step reaction carries high production intensity, reduces the unit consumption of initiator, dispersant and terminator "（The change of Xue, Shao Ping, peak chloroethene
Alkene polymerization reaction late stage adds chloroethylene polymerization reaction polyvinyl chloride, 4-11 pages of 3 phase in 1994）.But this is gathered for suspension method
For vinyl chloride production, and amount of monomer is added less than 10w/%.Also have document introduction " using the monomer for accounting for total addition 24%,
It is not homogenized, be directly added into polymeric kettle, that is, shorten polymerization time, and save homogenizing power "（Wang Manqing, Sun Zhen give birth to A-
21PVC pastes production of resins technology polyvinyl chloride, 20-23 pages of 2 phase in 2001）.But in text and undeclared add vinyl chloride monomer
Time and rate more without controlling the measure of final products grain size, therefore do not possess operability.
The content of the invention
It is an object of the invention to provide a kind of raising micro suspension polychlorostyrene that can mitigate viscous kettle degree, reduce auxiliary agent consumption
The method that ethylene pastes production of resins efficiency.
The present invention adopts the following technical scheme that：
A kind of method for improving micro suspension PVC paste resin production efficiency, carries out as follows：By initiator, breast
Polymeric kettle is added in after agent, assistant for emulsifying agent, vinyl chloride monomer and desalination water emulsification, is reacted at 40 DEG C~60 DEG C, reaction starts
30, to after sixty minutes, add vinyl chloride monomer.
Using above-mentioned technical proposal compared with prior art, the present invention with mitigate viscous kettle degree, improve production efficiency,
Reduce auxiliary agent consumption, and particle diameter and particle diameter distribution（Span）By intermediate addition amount of monomer and speed control can be added in
Advantage.Solve the problems, such as that the matter homogenizing time is longer in current PVC paste resin production so that material particular diameter after homogenizing
Not only meet process requirements but also emulsion droplets stable and product cut size and grain size point are still ensured that after vinyl chloride monomer is added
Cloth substantially reduces homogenising time, improves production efficiency in suitable scope.
The present invention preferred embodiment be：
This five kinds of substances of initiator, emulsifier, assistant for emulsifying agent, vinyl chloride monomer and desalted water are matched somebody with somebody by following quality
Than：Initiator accounts for the 0.01~0.3% of vinyl chloride monomer quality, and emulsifier accounts for the 0.2~0.8% of vinyl chloride monomer quality；Help breast
Agent accounts for the 1.0~2.5% of vinyl chloride monomer quality；Soft water accounts for the 100~105% of vinyl chloride monomer quality.
Initiator is peroxide α, α '-bis-（Neodecanoic acid）Diisopropylbenzene (DIPB) base ester, peroxidating neodecanoic acid cumyl ester, peroxidating
Two carbonic acid di-n-propyl esters, di-isopropyl peroxydicarbonate, peroxidating neodecanoic acid -1,1,3,3- tetramethyls butyl ester, peroxidating two
Carbonic acid two（4- tert-butylcyclohexyls）Ester, peroxidating neodecanoic acid（1- cyclohexyl -1- methyl）Ethyl ester, dicetyl peroxydicarbonate two（2-
Ethyoxyl）Ethyl ester, dicetyl peroxydicarbonate two（2- ethyls）The tertiary own ester of own ester, peroxidating neodecanoic acid, dicetyl peroxydicarbonate dimethoxy
Base butyl ester, dicetyl peroxydicarbonate two（3- methyl -3- methoxybutyls）Ester, new peroxide tert-butyl caprate, peroxidating neopentanoic acid
Tertiary own ester and azo compound；Initiator is one or more multiplexings.
Emulsifier is neopelex, lauryl sodium sulfate, potassium oleate, N- cetyls-N-ethylmorpholine
One or more of ethyl alcohol base ammonium sulfate, polyoxyethylene monostearate or octylphenol ether.
Assistant for emulsifying agent is one or more of hexadecanol, octadecyl alcolol or stearic acid.
Initiator, emulsifier, assistant for emulsifying agent, vinyl chloride monomer and desalted water are sufficiently stirred in closed mixing channel mixed
It closes, 2~5kw/m of power of agitator3, after mixing operation emulsification is carried out in mulser, add in reaction kettle and reacted.
Material after mixing is emulsified with the homogenizer of two series connection, material after mixing initially enters
First mulser is emulsified, and the material after the emulsification of First mulser is emulsified again into second mulser, so
Reaction kettle is added in afterwards carries out polymerisation.
After reaction starts, vinyl chloride monomer is added with following speed：
In formula：Kg/ points of dW-plus monomer rate；Kj/ points of the heat that Q-reaction kettle removes；Vinyl chloride under d-reaction temperature
The density kg/m of monomer3；The hot kj/kg of 1600-polymerization of vinyl choride monomer；The density kg/m of 1400-polyvinyl chloride3。
The amount for adding vinyl chloride monomer is to account for initial reaction stage adds in quality 5~30%.
Emulsifier accounts for vinyl chloride monomer quality 0.3~0.5%；Assistant for emulsifying agent accounts for the 1.5~2.0% of vinyl chloride monomer quality；
Initiator amount is the 0.04~0.10% of vinyl chloride monomer quality.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
In figure：Add vinyl chloride monomer feed pump 1, premix slot 2, premix slot agitating device 3, rear pump 4, three-way valve 5,
Polymerization reaction kettle 6.
Specific embodiment
By vinyl chloride monomer, desalted water, initiator（Oil-soluble initiator）, emulsifier aqueous solution（One in desalted water
Divide to add in emulsifier and be configured to aqueous solution, in favor of by being pumped into premix slot）It is added in other auxiliary agents in premix slot, object
Material starts scattered pump, material warp in premix slot through premixing slot blender stirring 20 after forty minutes, after preferably 30 minutes
Enter two mulsers of tandem after scattered pump is scattered, between narrow between mulser multi-layer rotor and stator of material
High-speed motion in gap makes material dispersion evenly by mulser, material is made to be held in working chamber under the action of special construction
By hundreds of thousands per minute time or even the high speed shear of up to a million times, strong aquashear and turbulent flow are formd, while makes material
Generate centrifugation, squeeze, grinding, collision, the comprehensive functions power such as crush coordination under obtain fully dispersed, homogeneous, emulsification, broken
The technological requirements such as broken, refinement, mixing.Realize collection scattered, homogeneous, broken, emulsification, mixing, dissolving, suspend, conveying etc. is one
The purpose of body.Using scattered pump, the homogenising time of material is shortened.After material is homogenized, into polymeric kettle.So add in
A lotion part in kettle only emulsifies minimum for 2 times, and some emulsification 3 times, 4 times ... n times, emulsifying power double.It protects
Initial emulsification liquid-drop diameter is demonstrate,proved between 0.1~1.0 μm, final products resin grain size and particle diameter distribution are met the requirements.
Mulser form is not strict with, stator rotor homogenizer, colloid mill, high cutting homogenizer and high-pressure emulsification machine
Deng as long as can reach required liquid-drop diameter, the homogenizer forms of two series connection may be the same or different.
Premixing slot agitator type, there is no stringent limitation, propeller type, flat paddle formula, oblique paddle, three leaf swept-backs, anchor formulas
Deng, but stir necessary strong.It is required that 2.0~5.0KW/m of stirred volume power bracket3, preferably in 3.0~4.0 KW/m3。
If summation watt rating is less than 2.0KW/m3, stirring efficiency is poor, if above 5.0KW/m3, energy consumption is excessively high；As long as ensure higher object
Expect the efficiency of stirring.
Desalted water accounts for the 100~105% of vinyl chloride monomer quality.
Oil-soluble initiator includes：Initiator is peroxide α, α '-bis-（Neodecanoic acid）Diisopropylbenzene (DIPB) base ester, peroxidating are new
Capric acid cumyl ester, peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxidating neodecanoic acid -1,1,3,3- four
Methylbutyl butenoate, dicetyl peroxydicarbonate two（4- tert-butylcyclohexyls）Ester, peroxidating neodecanoic acid（1- cyclohexyl -1- methyl）Ethyl ester,
Dicetyl peroxydicarbonate two（2- ethyoxyls）Ethyl ester, dicetyl peroxydicarbonate two（2- ethyls）The tertiary own ester of own ester, peroxidating neodecanoic acid, mistake
Aoxidize two carbonic acid dimethoxy butyl esters, dicetyl peroxydicarbonate two（3- methyl -3- methoxybutyls）Ester, the tertiary fourth of peroxidating neodecanoic acid
The tertiary own ester of ester, peroxidating neopentanoic acid and azo compound；Such as two isobutyric acid of azobisisoheptonitrile, azodiisobutyronitrile and azo
Dimethyl ester etc., but not limited to this；Initiator can be that single one kind can also be two or more multiplexings；Initiator amount is
0.01~0.3w/% of vinyl chloride monomer quality, preferably 0.04~0.10w/%.
Emulsifier includes：Neopelex, lauryl sodium sulfate, potassium oleate, N- cetyl N ethyl morpholines
Ethyl alcohol base ammonium sulfate, polyoxyethylene monostearate, octylphenol ether etc.；Can be that single one kind can also be two or more
Multiplexing.Emulsifier accounts for the 0.2~0.8% of vinyl chloride monomer quality, preferably accounts for vinyl chloride monomer quality 0.3~0.5%.
Assistant for emulsifying agent includes hexadecanol, octadecyl alcolol, stearic acid etc..Assistant for emulsifying agent can be applied alone or two kinds or more
Kind multiplexing.Assistant for emulsifying agent accounts for the 1.0~2.5% of vinyl chloride monomer quality, preferably account for vinyl chloride monomer quality 1.5~
2.0%。
The model of microsuspending method vinyl chloride resin is divided according to the degree of polymerization, and the degree of polymerization is the letter of reaction temperature
Number, therefore the resin of each model corresponds to a specific reaction temperature.Polymerisation is exothermic again, reaction heat and
When remove, just can guarantee that polymerisation is reacted at a constant temperature.The usually corresponding polymerization temperature of microsuspending method vinyl chloride resin
Scope is that the density of vinyl chloride under 40-60 DEG C of different temperatures is as follows：
| Temperature（℃） | 40 | 45 | 50 | 55 | 60 |
| Density（kg/m3） | 872.1 | 862.0 | 851.7 | 841.3 | 830.7 |
The density of Corvic is 1400kg/m3, with the continuous progress that chloroethylene polymerization reacts, object in polymeric kettle
Material volume is shunk.The heat transfer area of reaction kettle is reduced, and is moved thermal energy power and is declined, production capacity reduces；Due to volume contraction, make in kettle
Gas-phase space increases, and viscous kettle most easily occurs for gas-liquid interface, and kettle pasting matter declines the quality of product.The present invention passes through into polymeric kettle
Polyvinyl chloride monomer is added, the volume of material in kettle is made to remain unchanged to overcome above-mentioned deficiency.
When in 30 minutes that reaction starts, decomposition of initiator is there are one longer induction period, and reaction speed is low, volume contraction
Rate is very low, the danger that this stage, which begins to add vinyl chloride monomer, to be had " full kettle ", if adding list again more than 60 minutes in reaction
Body influences to have started to show caused by volume contraction.So adding the monomer time is selected in reaction beginning 30~60 minutes, polymerization is anti-
Normal reaction speed should be basically reached to carry out afterwards.
Pass through the flow of cooling water in polymeric kettle cooling jacket and cooling and stirring（) and inlet water temperature W（T1), exit water temperature
(T2) difference, can obtain the rate of heat release of polymerisation, and then acquire cubical contraction, determine the addition speed of vinyl chloride monomer
Rate.
Rate of heat release Q=WC (T2-T1) of polymerisation
In formula：Q- polymerisation rate of heat releases（Kj/ points）；W- cooling water flows（Kg/ points）；Specific heat (the 4.2kj/ of C- water
kg.℃)
Cubical contraction in reaction process：
In formula：DV-volume contraction rate m3/ point；Kj/ points of the heat that Q-reaction kettle removes；Chloroethene under d-reaction temperature
The density kg/m of alkene monomer3；The hot kj/kg of 1600-polymerization of vinyl choride monomer；The density kg/m of 1400-polyvinyl chloride3。
Add in the maximum rate of vinyl chloride monomer
In formula：Kg/ points of dW-plus monomer rate；Kj/ points of the heat that Q-reaction kettle removes；Vinyl chloride under d-reaction temperature
The density kg/m of monomer3；The hot kj/kg of 1600-polymerization of vinyl choride monomer；The density kg/m of 1400-polyvinyl chloride3。
The danger that if rate for adding vinyl chloride monomer, which is more than maximum rate, to be had " full kettle ".
The amount that vinyl chloride monomer is added into polymeric kettle is through emulsifying the 5~30% of vinyl chloride monomer quality, if be less than
5w/% improves respond effect unobvious；If it exceeds the grain size that 30w/% obtains resin is exceeded, and the danger of " full kettle "
Increase.Due to only adding vinyl chloride monomer in reaction process, without increasing initiator, emulsifier and assistant for emulsifying agent, therefore auxiliary agent disappears
Consumption reduces, and production cost declines.
When pressure declines 0.2mpa in kettle（Table）When, conversion rate of vinyl chloride is about 90w/%, stops polymerisation；It is let out
Material, unreacted monomer recycling, spray drying, screening and packaging.
By vinyl chloride monomer：18.5 tons, peroxidating diethoxy ethyl ester 4.5kg, azobisisoheptonitrile 4.5Kg, desalted water
19 tons, lauryl sodium sulfate 125Kg, hexadecanol 210Kg；It adds in premixing tank, through 3.5kw/m3Power stirs, and adds in series connection
Two mulsers emulsification, add in polymeric kettle in, polymerisation, polymerization temperature 45 are carried out in 48 cubic metres of polymerization reaction kettles
DEG C, when reaction proceeds to 30min, jacket of polymerization and stirring cooling water inflow are respectively 200 and 60m3/ h imports and exports water temperature
Respectively 23 DEG C and 24.5 DEG C, acquiring rate of heat release is：
Q = WC(T2-T1) = （200 + 60）×1000×4.2（24.5-23）/ 60=27300kj/ points
Most greatly monomer rate should be：
dW = Q（1-d/1400）/1600 = 27300（1-862/1400)/1600=6.552kg/ points
Monomer feed pump 1 is started, vinyl chloride monomer 1000 minutes, total amount about 1850kg is added in 1.85kg/ points of speed,
Polymerization time is 1089 minutes, and reaction was completed after reaction pressure decline 0.2Mpa, carries out, from pressing and forcing to recycle, forcing recycling same
When add in thinner, kettle pressure is recycled to -0.05mpa, and recycling terminates, and discharges.
Latex obtains finished product 18,645kg through crushing after being dried with spray dryer, 3.568 μm of volume maximum particle diameter,
Span 2.225, average degree of polymerization 1615.
Embodiment 1：
By vinyl chloride monomer：18.5 tons, dicetyl peroxydicarbonate two（2- ethyoxyls）Second fat 4.5kg, azobisisoheptonitrile
4.5Kg, 19 tons of desalted water, lauryl sodium sulfate 125Kg, hexadecanol 210Kg；It adds in dispersion tank, through 3.5kw/m3Power
Stirring adds in two mulsers emulsification of series connection, adds in polymeric kettle, carries out polymerizeing in 48 cubic metres of polymerization reaction kettles anti-
Should, 45 DEG C of polymerization temperature, when reaction proceeds to 30min, jacket of polymerization and stirring cooling water inflow are respectively 200 m3/h
And 60m3/ h, inlet and outlet water temperature is respectively 23 and 24.5 DEG C, and acquiring rate of heat release is：
Q = WC(T2-T1) = （200 + 60）×1000×4.2（24.5-23）/ 60=27300kj/ points
Most greatly monomer rate should be：
dW = Q（1-d/1400）/1600 = 27300（1-862/1400)/1600=6.552kg/ points
Monomer feed pump 1 is started, vinyl chloride monomer 1000 minutes, total amount about 1850kg is added in 1.85kg/ points of speed,
Polymerization time is 1089 minutes, and reaction was completed after reaction pressure decline 0.2Mpa, carries out, from pressing and forcing to recycle, forcing recycling same
When add in thinner, kettle pressure is recycled to -0.05mpa, and recycling terminates, and discharges.
Latex obtains finished product 18645kg through crushing after being dried with spray dryer, 3.568 μm of volume maximum particle diameter,
Span 2.225, average degree of polymerization 1615.
Embodiment 2：
By 20 tons of vinyl chloride monomer, dicetyl peroxydicarbonate two（2- ethyoxyls）Second fat 5.5kg, azobisisoheptonitrile 4.5Kg,
21 tons of desalted water, lauryl sodium sulfate 200Kg, hexadecanol 260Kg；It adds in dispersion tank, through 3.0kw/m3Power stirs, and adds
Enter two mulsers emulsification of series connection, add in polymeric kettle, polymerisation, polymerization temperature are carried out in 48 cubic metres of polymerization reaction kettles
It spends for 45 DEG C, when reaction proceeds to 45min, jacket of polymerization and stirring cooling water inflow are respectively 187 m3/ h and 64m3/ h,
It is respectively 23 and 24.4 DEG C to import and export water temperature, and acquiring rate of heat release is：
Q = WC(T2-T1) = （187 + 64）×1000×4.2（24.4-23）/ 60=24598kj/ points
Most greatly monomer rate should be：
dW = Q×（1-d/1400）/1600= 24598（1-862/1400)/1600=5.904kg/ points
Monomer feed pump 1 is started, vinyl chloride monomer 950 minutes, total amount about 4000kg is added in 4.21kg/ points of speed,
Polymerization time is 1010 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing recycling, forcing recycling
Thinner is added in simultaneously, kettle pressure is recycled to -0.05mpa, and recycling terminates, and discharges.
Latex obtains finished product 22050kg through crushing after being dried with spray dryer, 3.974 μm of volume maximum particle diameter,
Span 3.125, average degree of polymerization 1595.
Embodiment 3：
By 20 tons of vinyl chloride monomer, dicetyl peroxydicarbonate two（2- ethyoxyls）Second fat 5.5kg, azobisisoheptonitrile 4.5Kg,
20 tons of desalted water, lauryl sodium sulfate 100Kg, hexadecanol 160Kg；It adds in dispersion tank, through 4.5kw/m3Power stirs, and adds
Enter two mulsers emulsification of series connection, add in polymeric kettle, polymerisation, polymerization temperature are carried out in 48 cubic metres of polymerization reaction kettles
45 DEG C of degree, when reaction proceeds to 50min, when reaction proceeds to 30min, jacket of polymerization and baffle cooling water inflow difference
For 213 and 61m3/ h, inlet and outlet water temperature is respectively 23.2 and 24.6 DEG C, and acquiring rate of heat release is：
Q = WC(T2-T1) = （213 + 61）×1000×4.2（24.6-23,2）/ 60=26852kj/ points
Most greatly monomer rate should be：
dW = Q×（1-d/1400）/1600=26852（1-862/1400)/1600=6.44kg/ points
Monomer feed pump 1 is started, vinyl chloride monomer 1090 minutes, total amount about 6000kg is added in 5.5kg/ points of speed,
Polymerization time is 1216 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing recycling, forcing recycling
Thinner is added in simultaneously, kettle pressure is recycled to -0.05mpa, and recycling terminates, and discharges.
Latex obtains finished product 23640kg through crushing after being dried with spray dryer, 4.128 μm of volume maximum particle diameter,
Span 2.635, average degree of polymerization 1658.
Normal microsuspending method PVC paste resin grain size is 0.5~5.0 μm, shows to add emulsification chloroethene in reaction process
Vinyl chloride of the alkene monomer weight below 30%, product cut size is in suitable scope.
From above 3 examples it can also be seen that, initiator type and dosage basically identical situation identical in reaction temperature
Under, reaction time variation is little, and yield but substantially increases, and improves production efficiency.
Embodiment 4：
By 18 tons of vinyl chloride monomer, peroxidating diethoxy ethyl ester 5.5kg, azodiisobutyronitrile 4.5Kg, desalted water 20
Ton, neopelex 150Kg, octadecyl alcolol 200Kg；It adds in premix slot, through 4.5kw/m3Power stirs, and adds in series connection
Two mulsers emulsification, add in polymeric kettle in, polymerisation, polymerization temperature 45 are carried out in 48 cubic metres of polymerization reaction kettles
DEG C, when reaction proceeds to 60min, jacket of polymerization and stirring cooling water inflow are respectively 202 m3/ h and 68m3/ h, inlet and outlet
Water temperature is respectively 22.6 DEG C and 24.3 DEG C, acquires rate of heat release and is：
Q = WC(T2-T1) = （202+68）×1000×4.2（24.3-22.6）/ 60=32130kj/ points
Most greatly monomer rate should be：
dW = Q×（1-d/1400）/1600=32130（1-862/1400)/1600=7.71kg/ points
Monomer feed pump 1 is started, vinyl chloride monomer 860 minutes, total amount about 5800kg is added in 6.8kg/ points of speed, is gathered
It is 1192 minutes to close the time.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing recycling, forcing recycling same
When add in thinner, kettle pressure is recycled to -0.05mpa, and recycling terminates, and discharges.
Latex obtains finished product 21720kg through crushing after being dried with spray dryer, 4.026 μm of volume average particle size,
Span 2.545, average degree of polymerization 1671.
Embodiment 5：
By 18 tons of vinyl chloride monomer, peroxy dicarbonate di-n-propyl ester 5.5kg, azobisisoheptonitrile 4.5Kg, desalted water 20
Ton, lauryl sodium sulfate 150Kg, hexadecanol 200Kg；It adds in premix slot, through 4.5kw/m3Power stirs, and adds in series connection
The emulsification of two mulsers, adds in polymeric kettle, carries out polymerisation in 48 cubic metres of polymerization reaction kettles, 45 DEG C of polymerization temperature,
When reaction proceeds to 30min, jacket of polymerization and stirring cooling water inflow are respectively 190 and 63m3/h, and inlet and outlet water temperature is distinguished
For 23 DEG C and 24.6 DEG C, acquiring rate of heat release is：
Q = WC(T2-T1) = （190 + 63）×1000×4.2（24.6-23）/ 60=28336kj/ points
Most greatly monomer rate should be：
dW = Q×（1-d/1400）/1600=28336（1-862/1400)/1600=6.80kg/ points
Monomer feed pump 1 is started, vinyl chloride monomer 980 minutes, total amount about 4900kg, polymerization are added in 5kg/ points of speed
Time is 1216 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing recycling, forcing recycling simultaneously
Thinner is added in, kettle pressure is recycled to -0.05mpa, and recycling terminates, and discharges.
Latex obtains finished product 21640kg through crushing after being dried with spray dryer, 3.876 μm of volume average particle size,
Span 2.335, average degree of polymerization 1705.
Embodiment 6
By 18.5 tons of vinyl chloride monomer, di-isopropyl peroxydicarbonate 5.5kg, azodiisobutyronitrile 4.5Kg, desalted water
20 tons, potassium oleate 150Kg, stearic acid 200Kg；It adds in premix slot 2, through 4.5kw/m3Power stirs, and adds in two of series connection
Mulser emulsifies, and adds in polymerization reaction kettle 6, polymerisation, polymerization temperature 45 are carried out in 48 cubic metres of polymerization reaction kettles 6
DEG C, when reaction proceeds to 50min, 6 chuck of polymerization reaction kettle and stirring cooling water inflow are respectively 185 m3/ h and 61m3/ h, into
Exit water temperature is respectively 23.3 DEG C and 24.8 DEG C, acquires rate of heat release and is：
Q = WC(T2-T1)= （185 + 61）×1000×4.2（24.8-23.3）/ 60=25410kj/ points
Maximum chlorination vinyl monomer rate should be：
dW = Q×（1-d/1400）/1600=25410（1-862/1400)/1600=6.10kg/ points
Monomer feed pump 1 is started, vinyl chloride monomer 1000 minutes, total amount about 4500kg is added in 4.5kg/ points of speed,
Polymerization time is 1108 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing recycling, forcing recycling
Thinner is added in simultaneously, kettle pressure is recycled to -0.05mpa, and recycling terminates, and discharges.
Latex obtains finished product 22140kg through crushing after being dried with spray dryer, 3.167 μm of volume average particle size,
Span 2.607, average degree of polymerization 1697.
Claims (5)
1. a kind of method for improving micro suspension PVC paste resin production efficiency, carries out as follows：By initiator, emulsification
Polymeric kettle is added in after agent, assistant for emulsifying agent, vinyl chloride monomer and desalination water emulsification, is reacted at 40 DEG C~60 DEG C, reaction starts 30
To 60 minutes, vinyl chloride monomer is added with following speed：
In formula：Kg/ points of dW-plus monomer rate；Kj/ points of the heat that Q-reaction kettle removes；Vinyl chloride monomer under d-reaction temperature
Density kg/m3；The hot kj/kg of 1600-polymerization of vinyl choride monomer；The density kg/m of 1400-polyvinyl chloride3；Initiator, emulsification
This five kinds of substances of agent, assistant for emulsifying agent, vinyl chloride monomer and desalted water are matched by following quality：Initiator accounts for vinyl chloride monomer
The 0.01~0.3% of quality, emulsifier account for the 0.2~0.8% of vinyl chloride monomer quality；Assistant for emulsifying agent accounts for vinyl chloride monomer quality
1.0~2.5%；Soft water accounts for the 100~105% of vinyl chloride monomer quality；By initiator, emulsifier, assistant for emulsifying agent, vinyl chloride monomer
It is thoroughly mixed with desalted water in closed mixing channel, 2~5kw/m of power of agitator3, mixing operation is carried out in mulser
After emulsification, add in reaction kettle and reacted；Material after mixing with the homogenizer of two series connection is emulsified, is mixed
Material after uniformly initially enters First mulser and is emulsified, and the material after the emulsification of First mulser enters second
Mulser is emulsified again, is then added in reaction kettle and is carried out polymerisation；The amount for adding vinyl chloride monomer is to account for initial reaction stage to add
Enter the 5~30% of quality.
2. the method according to claim 1 for improving micro suspension PVC paste resin production efficiency, it is characterised in that：Draw
Agent is sent out as peroxide α, α '-bis-（Neodecanoic acid）Diisopropylbenzene (DIPB) base ester, peroxidating neodecanoic acid cumyl ester, dicetyl peroxydicarbonate two are just
Propyl ester, di-isopropyl peroxydicarbonate, peroxidating neodecanoic acid -1,1,3,3- tetramethyls butyl ester, dicetyl peroxydicarbonate two（Uncle 4-
Butylcyclohexyl）Ester, peroxidating neodecanoic acid（1- cyclohexyl -1- methyl）Ethyl ester, dicetyl peroxydicarbonate two（2- ethyoxyls）Ethyl ester,
Dicetyl peroxydicarbonate two（2- ethyls）The tertiary own ester of own ester, peroxidating neodecanoic acid, dicetyl peroxydicarbonate dimethoxy butyl ester, peroxidating
Two carbonic acid two（3- methyl -3- methoxybutyls）The tertiary own ester of ester, new peroxide tert-butyl caprate, peroxidating neopentanoic acid and azo
Compound；Initiator is one or more multiplexings.
3. the method according to claim 1 for improving micro suspension PVC paste resin production efficiency, it is characterised in that：Breast
Agent is neopelex, lauryl sodium sulfate, potassium oleate, N- cetyls-N-ethylmorpholine ethyl alcohol base sulfuric acid
One or more of ammonium, polyoxyethylene monostearate or octylphenol ether.
4. the method according to claim 1 for improving micro suspension PVC paste resin production efficiency, it is characterised in that：It helps
Emulsifier is one or more of hexadecanol, octadecyl alcolol or stearic acid.
5. the method according to claim 1 for improving micro suspension PVC paste resin production efficiency, it is characterised in that：Breast
Agent accounts for vinyl chloride monomer quality 0.3~0.5%；Assistant for emulsifying agent accounts for the 1.5~2.0% of vinyl chloride monomer quality；Initiator amount
It is the 0.04~0.10% of vinyl chloride monomer quality.
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| CN106749796A (en) * | 2016-11-30 | 2017-05-31 | 唐山三友氯碱有限责任公司 | Microsuspending method method for producing PVC paste resin |
| CN107141386A (en) * | 2017-06-16 | 2017-09-08 | 唐山三友氯碱有限责任公司 | A kind of method for producing PVC paste resin and reaction retracting device |
| CN110372890A (en) * | 2018-04-13 | 2019-10-25 | 台湾塑胶工业股份有限公司 | PVC emulsifying powder, its manufacturing method and its application |
| CN109173965A (en) * | 2018-10-09 | 2019-01-11 | 天津渤化工程有限公司 | Emulsion method pastes the closed continuous producing apparatus of resin device and method |
| CN111234076A (en) * | 2020-03-31 | 2020-06-05 | 新疆中泰化学阜康能源有限公司 | Disposable glove material of polyvinyl chloride paste resin and production method and application thereof |
| CN114539454A (en) * | 2020-11-24 | 2022-05-27 | 江苏康宁化学有限公司 | Preparation method of polyvinyl chloride paste resin |
| CN112590315A (en) * | 2020-12-28 | 2021-04-02 | 福建鹏达包装材料有限公司 | Preparation method of barrier composite film for frozen packaging |
| CN113278099A (en) * | 2021-05-25 | 2021-08-20 | 扬州工业职业技术学院 | Preparation method of self-plasticizing polyvinyl chloride resin |
| CN114573740A (en) * | 2022-03-02 | 2022-06-03 | 沈阳化工股份有限公司 | PVC paste resin and preparation method thereof |
| CN116355488B (en) * | 2022-12-02 | 2024-02-06 | 鄂尔多斯市瀚博科技有限公司 | Continuous flow production process of anti-sticking kettle agent |
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