CN105884945A - Method for improving production efficiency of micro-suspension polyvinyl chloride paste resin - Google Patents
Method for improving production efficiency of micro-suspension polyvinyl chloride paste resin Download PDFInfo
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- CN105884945A CN105884945A CN201610492338.2A CN201610492338A CN105884945A CN 105884945 A CN105884945 A CN 105884945A CN 201610492338 A CN201610492338 A CN 201610492338A CN 105884945 A CN105884945 A CN 105884945A
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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 invention relates to a production method of polyvinyl chloride paste resin, in particular to a method for improving production efficiency of micro-suspension polyvinyl chloride paste resin. The method comprises the following steps: emulsifying an initiator, an emulsifier, a co-emulsifier, a vinyl chloride monomer and desalted water, then adding into a polymerization kettle, reacting at the temperature of 40-60 DEG C, and replenishing the vinyl chloride monomer after the reaction is carried out for 30-60 minutes. Compared with the prior art, the method has the advantages that fouling degree is reduced, production efficiency is improved, consumption of auxiliaries is reduced and particle size and particle size distribution can be controlled by virtue of amount of the monomer added in the production process and adding rate; and the problem that material homogenizing time is relatively long during the current polyvinyl chloride paste resin production is solved, the particle size of the homogenized material meets process requirements, and stable emulsion liquid drops and appropriate product particle size range and particle size distribution range can be still guaranteed after the polyvinyl chloride monomer is replenished, so that homogenizing time is shortened, and production efficiency is improved.
Description
Technical field
The present invention relates to the production method of a kind of PVC paste resin, particularly a kind of raising micro suspension Welvic
The method of production of resins efficiency.
Background technology
Polyvinyl chloride (PVC) sticks with paste resin as the term suggests being that this kind of resin is mainly applied making paste forms, Ren Menchang
Stick with paste with this kind and be referred to as plasticized paste, be a kind of unique liquid form of igelite under rough.Stick with paste resin often by
Emulsion and microsuspending method prepare.
PVC paste resin is fine because of granularity, and its quality, as talcum powder, has nonflowing character.PVC paste resin is same
It is agitated to form stable suspension after plasticizer mixing, i.e. makes PVC paste material, or referred to as PVC plasticized paste, PVC colloidal sol, and
People are used for being processed into end article the most in this form.During paste producing, according to different goods needs, add various
Filler, diluent, heat stabilizer, foaming agent and light stabilizer etc..
The development of PVC paste Resin Industry, it is provided that the most heated a kind of novel liquid just becoming polrvinyl chloride product
Material.The configuration of this kind of liquid material is convenient, and stable performance, easy to control, easy to use, product properties is excellent, chemical stability is good,
There are certain mechanical strength, easy coloring etc., be therefore widely used in artificial leather, flooring laminate, medical, precision instrument produce and
Industry (electronic handle medicine equipment, labour protection hand are moulded in the elastomeric glove of catering trade, vinyl toy, soft trade mark, wallpaper, leaching
Set etc.), paint, foamed plastic, conveyer belt, the production of automobile decoration etc..
Compared with traditional suspending resin, PVC paste resin has the advantage that
(1) process equipment is inexpensive；(2) mould simple cheap；(3) can be made into F-SP；(4) foaming is easily；(5) goods are heated
Number of times is few, it is possible to a small amount of, multi items produces.
Whole world paste PVC resin industry develops with fast speed always, and the most nearly ten years, production capacity and yield are jump
Formula increases, and increases especially pronounced in Asia.2014, polyvinyl chloride resin aggregated capacity about 5,500,000 tons/year, China's production capacity were stuck with paste in the whole world
About 710,000 tons, account for whole world aggregated capacity 13%.
Preparation method mainly has:
1, emulsion method
Emulsion polymerization formula mainly has VCM, water, water soluble starter and emulsifying agent.Stirring is required very strict by emulsion polymerization, draws
Outbreak is carried out with in aqueous phase, and normally used initiator is the redox system of water soluble persulfates and sulphite
System, reaction speed is relevant with the addition speed of reducing agent and amount.Generally, the latex particle size that emulsion polymerization obtains is less than
0.2 μm, in order to reach to increase the purpose of latex particle size, develops emulsion seeded polymerization, makes latex particle size increase to 1.0 μm left
Right.In emulsion is polymerized, if with the presence of the high polymer latex generated, controlling material proportion and condition, VCM is only in principle
The latex particle generated is polymerized, and no longer forms new particle；This high polymer latex generated just looks like crystal seed,
Because being referred to herein as " emulsion seeding polymerization.Not only there is rational particle diameter, it is necessary to there is suitable particle diameter distribution, just can obtaining property
The PVC paste resin that energy is excellent.In emulsion polymerization, emulsifying agent is critically important, and quantity used determines the population of initiator, and to
The size of whole latex particle has played Main Function.Especially when carrying out seed and generating, use high trigger rate and low concentration breast
Agent produces, and present latex particulate Size Distribution can be made to narrow.
2, microsuspending method
Microsuspension polymerization is to prepare a kind of method that PVC paste resin is newer, and its flow process is: first by VCM, oil-soluble initiator, breast
The method of agent and water mechanical homogenization makes stable emulsus (particle diameter is about 1.0 μm), is then polymerized.Use this side
The mobility of the PVC paste resin that method produces is excellent, and emulsifier is few, and heat endurance and the water-resistance of resin are all changed
Kind.This production technology need to pay special attention to following influence factor: selects suitable compound emulsifying agent and particle modifying agent system；
The homogenizing of polymerization system component；Mixing speed；Water is appropriate with the ratio of monomer.It is the most widely used side 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 is divided into chemicals to prepare, be polymerized, reclaim blowing, be spray-dried classification, pulverizing,
Several operations such as sewage automatically processes continuously.
Chemicals is prepared: to be fed after being configured with hot water by the auxiliary agent such as emulsifying agent, assistant for emulsifying agent etc., pure water during charging,
Initiator, is simultaneously introduced in tank diameter, adds the chemicals after configuration well successively and adds after VCM adds in the effect disperseing pump again
Under be circulated in tank diameter, make material dispersion become stable fine droplet.According to establishment flow to after again turn trough enter to polymerization
In still.
Polymerization: when being dispersed through after the scattered feed liquid of pump fully enters polymeric kettle, polymeric kettle starts to warm up polymerization, due to polymerization
Reaction is exothermic reaction, it is necessary to removed by reaction heat in time.Thus it is guaranteed that the supply of jacketed low-temperature water is to maintain polymerization normal anti-
The key answered.When pressure raises, and reaction temperature reduces, proved response terminates, and starts to be discharged to when pressure is down to 4Kg/cm2
Blowpit carries out the recovery of VCM simultaneously.
Reclaim blowing: first carry out from pushing back receipts, when in still, pressure reaches 0.05mpa(table), after blowing is complete, polymeric kettle is entered
Row vacuumizes, and proceeds to force to reclaim, steam blowing, vinyl chloride in thorough Ex-all still, opens kettle cover and carry out high-pressure wash, clearly
Carry out after washing spraying and pipeline cleaning.After covering kettle cover, vacuumizing polymeric kettle and steam blowing, in removing still, air is gone forward side by side
Row leak test checks, with VCM vacuum breaker, vacuumizes again, adds VCM and reach 0.05mpa(table to pressure in still), right
Polymeric kettle carries out anti-stick still agent spraying, complete rear wait next still charging.
There is a lot of deficiency and make plant capacity low in traditional technique, product quality is the best, and cost remains high.
First it is homogenizing.PVC paste resin particle size different apparent density, mobility to resin, transport, pack and should
With all having a significant impact.Therefore must assure that the particle diameter of PVC paste resin within the specific limits and to be evenly distributed.PVC paste tree
The particle diameter of fat is largely determined by the size of vinyl chloride drop.General microsuspending method chloroethylene polymerization, monomer to be dispersed into
The drop of 0.1 2.0 μm, and keep stable in whole polymerization process.Except selecting suitable emulsifying agent and assistant for emulsifying agent,
Homogenizing is crucial.Generally vinyl chloride microsuspension polymerization homogenization process be by VCM monomer, deionized water, emulsifying agent and assistant for emulsifying agent,
Initiator and other auxiliary agents etc. are disposable to add in premix groove, is sufficiently stirred for making material premix.Then after making premix with homogenizer
Material under fierce mechanical shear stress effect, be emulsified into the emulsion of appropriate particle size.After general circulation continuously 30 minutes, 2/3
Emulsion continue cycling through, the emulsion of 1/3 enters still continuously.Emulsification times is long, and production efficiency is low.So add the emulsion one in still
Dividing only emulsification 1 time, some emulsification 2 times, 3 times ... n time, in emulsion, the particle diameter of drop and the particle diameter of final resin are uneven
Even, affect use and the processing characteristics of goods；
Another factor affecting production efficiency and product quality is exactly that the space of reactor can not get sufficiently utilizing.Due to chlorine
Bigger density contrast is there is, along with constantly carrying out of polymerisation, thing in polymeric kettle between vinyl monomer and Corvic
Significantly shrinking occurs in material volume, and the heat transfer area of reactor reduces, and moves heat energy power and declines, and production capacity reduces；Due to volume contraction,
In making still, gas-phase space increases, and gas-liquid interface the most easily occurs viscous still, and kettle pasting matter makes the Quality Down of product.In order to overcome this point
" phase adds a certain amount of VCM after polymerisation, and initiator remaining in making full use of still is the most anti-to have document to propose
Should, carry high production intensity, reduce initiator, dispersant and the unit consumption of terminator " (Xue Zhihua, Shao Ping, a peak chloroethylene polymerization
The reaction later stage adds chloroethylene polymerization reaction polyvinyl chloride, 3 phase in 1994 4-11 page).But this is for suspension type polyvinyl-chloride
For production, and add amount of monomer less than 10w/%.Also " use accounts for the monomer of total addition 24%, without all document introduction
Change, be directly added in polymeric kettle, i.e. shorten polymerization time, save again homogenizing power " (Wang Manqing, Sun Zhen are raw, and A-21PVC sticks with paste
Production of resins technology polyvinyl chloride, phase calendar year 2001 2 20-23 page).But in literary composition and the undeclared time adding VCM and speed
Rate, does not more control the measure of final products particle diameter, does not the most possess operability.
Summary of the invention
It is an object of the invention to provide a kind of can alleviate viscous still degree, reduce auxiliary agent consume raising micro suspension polychlorostyrene
The method of production of resins efficiency stuck with paste by ethene.
The present invention adopts the following technical scheme that
A kind of method improving micro suspension PVC paste resin production efficiency, is carried out as follows: by initiator, emulsification
Add polymeric kettle after agent, assistant for emulsifying agent, VCM and desalted water emulsification, react at 40 DEG C～60 DEG C, react beginning 30
After 60 minutes, add VCM.
Use technique scheme the present invention compared with prior art, have alleviate viscous still degree, improve production efficiency,
Reduce auxiliary agent consumption, and particle diameter and particle diameter distribution (span) can add amount of monomer by centre and add what speed controlled
Advantage.Solve the problem that during current PVC paste resin produces, the matter homogenizing time is longer so that material particular diameter after homogenizing
Not only meet process requirements but also after adding VCM, still ensure that emulsion droplets stable and product cut size and particle diameter divide
Cloth, in suitable scope, substantially reduces homogenising time, improves production efficiency.
The preferred version of the present invention is:
These five kinds of materials of initiator, emulsifying agent, assistant for emulsifying agent, VCM and desalted water carry out proportioning by following quality: draw
Sending out agent and account for the 0.01～0.3% of VCM quality, emulsifying agent accounts for the 0.2～0.8% of VCM quality；Assistant for emulsifying agent accounts for
The 1.0～2.5% of VCM weight；Soft water accounts for the 100～105% of VCM weight.
Initiator for including peroxide such as α, α '-bis-(neodecanoic acid) diisopropylbenzyl ester, peroxidating neodecanoic acid cumyl ester,
Peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (2-2 epoxide second fat), di-isopropyl peroxydicarbonate, peroxidating
Neodecanoic acid 1,1,3,3-tetramethyl butyl ester, peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxidating neodecanoic acid 1-hexamethylene
Base-1 Methylethyl, peroxy dicarbonate two-2 ethoxy ethyl ester, peroxy dicarbonate two-2 Octyl Nitrite, peroxidating neodecanoic acid
Tertiary own ester, peroxy dicarbonate dimethoxy butyl ester, peroxy dicarbonate two (3-methyl-3 methoxybutyl) ester, peroxidating are new
The capric acid tert-butyl ester, the peroxidating tertiary own ester of neopentanoic acid etc. and azo compound；Initiator；Be single one can also be two kinds
Or multiple multiplexing.
Emulsifying agent is neopelex, lauryl sodium sulfate, potassium oleate, N-cetyl N ethyl morpholine second
Alcohol radical ammonium sulfate, polyoxyethylene monostearate or octylphenol ether, kind therein or several.
Assistant for emulsifying agent be hexadecanol, octadecyl alcolol or stearic acid therein one or more.
It is sufficiently stirred for mixing in airtight mixing channel by initiator, emulsifying agent, assistant for emulsifying agent, VCM and desalted water
Close, power of agitator 2～5kw/m3, after carrying out mixing operation emulsification in mulser, react in adding reactor.
Material after the mixing homogenizer of two series connection emulsifies, and the material after mixing initially enters
First mulser emulsifies, and the material after First mulser emulsifies enters second mulser and emulsifies, so again
Rear addition reactor carries out polymerisation.
After reaction starts, add VCM with following speed:
In formula: dW adds monomer speed kg/ and divides；The heat kj/ of Q reactor removal divides；VCM under d reaction temperature
Density kg/m3；The 1600 hot kj/kg of polymerization of vinyl choride monomer；Density kg/m of 1400 polyvinyl chloride3。
The amount adding VCM is to account for initial reaction stage to add the 5～30w/% of quality.
Emulsifying agent accounts for VCM quality 0.3～0.5%；Assistant for emulsifying agent accounts for the 1.5～2.0% of VCM weight；
Initiator amount is the 0.04～0.10w/% of VCM quality.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention.
In figure: add VCM feed pump 1, premix groove 2, premix groove agitating device 3, rear pump 4, three-way valve 5,
Polymerization reaction kettle 6.
Detailed description of the invention
By VCM, desalted water, initiator (oil-soluble initiator), emulsifier aqueous solution (in desalted water
Point add in emulsifying agent and to be configured to the aqueous solution, be beneficial to by being pumped in premix groove) and other auxiliary agents add and premix in groove, thing
Expect, in premixing groove after premix groove agitator stirs 20 40 minutes, after preferably 30 minutes, to start dispersion pump, material warp
Two mulsers of tandem are entered, between narrow between mulser multi-layer rotor and stator of material after dispersion pump dispersion
High-speed motion in gap, makes material dispersion evenly by mulser, makes material hold in working chamber under the effect of special construction
By hundreds of thousands per minute time secondary high speed shear the most up to a million, define strong aquashear and turbulent flow, make material simultaneously
Produce be centrifuged, extrude, grind, collide, obtain under the coordination of the comprehensive function power such as pulverizing fully dispersed, homogeneous, emulsify, broken
Broken, refine, the technological requirement such as mixing.Achieve collection dispersion, homogeneous, crush, emulsify, mix, dissolve, suspend, conveying etc. is one
The purpose of body.Use dispersion pump, shorten the homogenising time of material.After material is homogenized, enter polymeric kettle.So add
It is 2 times that an emulsion part in still only emulsifies minimum, some emulsification 3 times, 4 times ... n time, emulsifying power doubles.Protect
Card initial emulsification liquid-drop diameter is between 0.1～1.0 μm, and final products resin particle diameter and particle diameter distribution meet requirement.
Mulser form is not strict with, stator rotor homogenizer, colloid mill, high cutting homogenizer and high-pressure emulsification machine
Deng, as long as required liquid-drop diameter can be reached, the homogenizer form of two series connection, can be identical, it is also possible to different.
Premix groove agitator type is the strictest to be limited, propeller type, flat paddle, oblique paddle, three leaf swept-backs, anchor formula
Deng, but stirring must be strong.Require stirred volume power bracket 2.0～5.0KW/m3, preferably at 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 too high；As long as ensureing higher thing
The efficiency of material stirring.
Desalted water accounts for the 100～105% of VCM quality.
Oil-soluble initiator includes: peroxide such as α, and α '-bis-(neodecanoic acid) diisopropylbenzyl ester, peroxidating neodecanoic acid are withered
Base ester, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (2-2 epoxide second fat), di-isopropyl peroxydicarbonate, mistake
Oxidation neodecanoic acid 1,1,3,3-tetramethyl butyl ester, peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxidating neodecanoic acid 1-
Cyclohexyl-1 Methylethyl, peroxy dicarbonate two-2 ethoxy ethyl ester, peroxy dicarbonate two-2 Octyl Nitrite, peroxidating are new
The tertiary own ester of capric acid, peroxy dicarbonate dimethoxy butyl ester, peroxy dicarbonate two (3-methyl-3 methoxybutyl) ester, peroxide
Change the neodecanoic acid tert-butyl ester, the peroxidating tertiary own ester of neopentanoic acid etc. and azo compound such as ABVN, azodiisobutyronitrile
With azo-bis-iso-dimethyl etc., but it is not limited to this；Initiator can be single one can also be that two or more are multiple
With；Initiator amount is the 0.01～0.3w/% of VCM quality, preferably 0.04～0.10w/%.
Emulsifying agent includes: neopelex, lauryl sodium sulfate, potassium oleate, N-cetyl N ethyl morpholine
Ethanol base ammonium sulfate, polyoxyethylene monostearate, octylphenol ether etc.；Can be single one can also be two or more
Multiplexing.Emulsifying agent accounts for the 0.2～0.8% of VCM quality, preferably accounts for VCM quality 0.3～0.5%.
Assistant for emulsifying agent includes hexadecanol, octadecyl alcolol, stearic acid etc..Assistant for emulsifying agent can be alone, it is also possible to is two kinds or many
Plant multiplexing.Assistant for emulsifying agent accounts for the 1.0～2.5% of VCM quality, preferably account for VCM weight 1.5～
2.0%。
The model of microsuspending method vinyl chloride resin divides according to the degree of polymerization, and the degree of polymerization is the letter of reaction temperature
Number, the therefore corresponding specific reaction temperature of the resin of each model.Polymerisation is again heat release, reaction heat and
Time removal, guarantee polymerisation is reacted at a constant temperature.The polymerization temperature that generally microsuspending method vinyl chloride resin is corresponding
Scope is 40-60 DEG C. under different temperatures, the density of vinyl chloride is as follows:
| Temperature (DEG C) | 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, along with constantly carrying out of chloroethylene polymerization reaction, material body in polymeric kettle
Long-pending occur shrinking.The heat transfer area of reactor reduces, and moves heat energy power and declines, and production capacity reduces；Due to volume contraction, make gas phase in still
Space increases, and gas-liquid interface the most easily occurs viscous still, and kettle pasting matter makes the Quality Down of product.The present invention is by adding in polymeric kettle
Polyvinyl chloride monomer, makes the volume of material in still keep constant to overcome above-mentioned deficiency.
When, in 30 minutes that reaction starts, decomposition of initiator has a longer induction period, and reaction speed is low, volume contraction
Rate is the lowest, and this stage begins to add VCM has the danger of " full still ", if adding list in reaction again more than 60 minutes
Body, the impact that volume contraction causes has started to manifest.So adding the monomer time to be selected in reaction beginning 30～60 minutes, polymerization is anti-
Carry out after should basically reaching normal reaction speed.
By polymeric kettle cooling jacket and cooling and stirring cool down flow (W) and inlet water temperature (T1), the exit water temperature of water
(T2) difference, can obtain the rate of heat release of polymerisation, and then try to achieve cubical contraction, determines the addition speed of VCM
Rate.
Rate of heat release Q of polymerisation=WC (T2-T1)
In formula: Q-polymerisation rate of heat release (kj/ divides)；W-cooling water flow (kg/ divides)；C-specific heat of water (4.2kj/kg.
℃)
Cubical contraction in course of reaction:
In formula: dV volume contraction speed m3/ point；The heat kj/ of Q reactor removal divides；Vinyl chloride list under d reaction temperature
Density kg/m of body3；The 1600 hot kj/kg of polymerization of vinyl choride monomer；Density kg/m of 1400 polyvinyl chloride3。
Add the maximum rate of VCM
In formula: dW adds monomer speed kg/ and divides；The heat kj/ of Q reactor removal divides；VCM under d reaction temperature
Density kg/m3；The 1600 hot kj/kg of polymerization of vinyl choride monomer；Density kg/m of 1400 polyvinyl chloride3。
The danger that if the speed adding VCM exceedes maximum rate to be had " full still ".
The amount adding VCM in polymeric kettle is through emulsifying the 5～30% of VCM quality, if be less than
5w/%, improves respond DeGrain；If it exceeds the particle diameter that 30w/% obtains resin exceeds standard, and the danger of " full still "
Increase.Owing to course of reaction only being added VCM, and do not increase initiator, emulsifying agent and assistant for emulsifying agent therefore auxiliary agent and disappear
Consumption reduces, and production cost declines.
When in still, pressure declines 0.2mpa(table) time, conversion rate of vinyl chloride is about 90w/%, stops polymerisation；Let out
Material, unreacted monomer reclaim, are spray-dried, sieve and pack.
By VCM: 18.5 tons, peroxidating diethoxy ethyl ester 4.5kg, ABVN 4.5Kg, desalted water
19 tons, lauryl sodium sulfate 125Kg, hexadecanol 210Kg；Add in premixing tank, through 3.5kw/m3Power stirs, and adds series connection
The emulsification of two mulsers, add in polymeric kettle, 48 cubic metres of polymerization reaction kettles carry out polymerisation, polymerization temperature 45
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
Being respectively 23 DEG C and 24.5 DEG C, trying to achieve rate of heat release is:
Q=WC (T2-T1)=(200+60) × 1000 × 4.2(24.5-23)/60=27300kj/ divides
Monomer speed should be the most greatly:
DW=Q(1-d/1400)/1600=27300(1-862/1400)/1600=6.552kg/ divides
Start monomer feed pump 1, add VCM 1000 minutes with the speed that 1.85kg/ divides, total amount about 1850kg, polymerization
Time is 1089 minutes, and reaction pressure declines end reaction after 0.2Mpa, carries out, from pressing and forcing to reclaim, forcing recovery to add simultaneously
Entering thinner, still pressure is recycled to-0.05mpa, and recovery terminates, and carries out discharging.
Latex spray dryer is the most size-reduced and obtains finished product 18,645kg, its volume maximum particle diameter 3.568 μm,
Span 2.225, average degree of polymerization 1615.
Embodiment 1:
By VCM: 18.5 tons, peroxy dicarbonate two (2-2 epoxide second fat) 4.5kg, ABVN 4.5Kg, de-
Salt solution 19 tons, lauryl sodium sulfate 125Kg, hexadecanol 210Kg；Add in dispersion tank, through 3.5kw/m3Power stirs, and adds
Two mulser emulsifications of series connection, add in polymeric kettle, carry out polymerisation, polymerization temperature in 48 cubic metres of polymerization reaction kettles
45 DEG C, when reaction proceeds to 30min, jacket of polymerization and stirring cooling water inflow are respectively 200 m3/ h and 60m3/ h, turnover
Saliva temperature is respectively 23 and 24.5 DEG C, tries to achieve rate of heat release and is:
Q=WC (T2-T1)=(200+60) × 1000 × 4.2(24.5-23)/60=27300kj/ divides
Monomer speed should be the most greatly:
DW=Q(1-d/1400)/1600=27300(1-862/1400)/1600=6.552kg/ divides
Start monomer feed pump 1, add VCM 1000 minutes with the speed that 1.85kg/ divides, total amount about 1850kg, polymerization
Time is 1089 minutes, and reaction pressure declines end reaction after 0.2Mpa, carries out, from pressing and forcing to reclaim, forcing recovery to add simultaneously
Entering thinner, still pressure is recycled to-0.05mpa, and recovery terminates, and carries out discharging.
Latex spray dryer is the most size-reduced and obtains finished product 18645kg, its volume maximum particle diameter 3.568 μm,
Span 2.225, average degree of polymerization 1615.
Embodiment 2:
By VCM 20 tons, peroxy dicarbonate two (2-2 epoxide second fat) 5.5kg, ABVN 4.5Kg, desalination
21 tons of water, lauryl sodium sulfate 200Kg, hexadecanol 260Kg；Add in dispersion tank, through 3.0kw/m3Power stirs, and adds string
Two mulser emulsifications of connection, add in polymeric kettle, carry out polymerisation in 48 cubic metres of polymerization reaction kettles, and polymerization temperature is
45 DEG C, when reaction proceeds to 45min, jacket of polymerization and stirring cooling water inflow are respectively 187 m3/ h and 64m3/ h, turnover
Saliva temperature is respectively 23 and 24.4 DEG C, tries to achieve rate of heat release and is:
Q=WC (T2-T1)=(187+64) × 1000 × 4.2(24.4-23)/60=24598kj/ divides
Monomer speed should be the most greatly:
DW=Q × (1-d/1400)/1600=24598(1-862/1400)/1600=5.904kg/ divides
Start monomer feed pump 1, add VCM 950 minutes with the speed that 4.21kg/ divides, total amount about 4000kg, polymerization
Time is 1010 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing to reclaim, forcing to reclaim simultaneously
Adding thinner, still pressure is recycled to-0.05mpa, and recovery terminates, and carries out discharging.
Latex spray dryer is the most size-reduced and obtains finished product 22050kg, its volume maximum particle diameter 3.974 μm,
Span 3.125, average degree of polymerization 1595.
Embodiment 3:
By VCM 20 tons, peroxy dicarbonate two (2-2 epoxide second fat) 5.5kg, ABVN 4.5Kg, desalination
20 tons of water, lauryl sodium sulfate 100Kg, hexadecanol 160Kg；Add in dispersion tank, through 4.5kw/m3Power stirs, and adds string
Two mulser emulsifications of connection, add in polymeric kettle, carry out polymerisation, polymerization temperature 45 in 48 cubic metres of polymerization reaction kettles
DEG C, when reaction proceeds to 50min, when reaction proceeds to 30min, jacket of polymerization and baffle plate cooling water inflow are respectively
213 and 61m3/ h, imports and exports water temperature and is respectively 23.2 and 24.6 DEG C, and trying to achieve rate of heat release is:
Q=WC (T2-T1)=(213+61) × 1000 × 4.2(24.6-23,2)/60=26852kj/ divides
Monomer speed should be the most greatly:
DW=Q × (1-d/1400)/1600=26852(1-862/1400)/1600=6.44kg/ divides
Start monomer feed pump 1, add VCM 1090 minutes with the speed that 5.5kg/ divides, total amount about 6000kg, polymerization
Time is 1216 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing to reclaim, forcing to reclaim simultaneously
Adding thinner, still pressure is recycled to-0.05mpa, and recovery terminates, and carries out discharging.
Latex spray dryer is the most size-reduced and obtains finished product 23640kg, its volume maximum particle diameter 4.128 μm,
Span 2.635, average degree of polymerization 1658.
Normal microsuspending method PVC paste resin particle diameter is 0.5～5.0 μm, shows to add emulsification chloroethene in course of reaction
The vinyl chloride of alkene monomer weight less than 30%, product cut size is in the range of suitably.
From above 3 examples it can also be seen that, identical in reaction temperature, initiator type and consumption basically identical situation
Under, reaction time change is little, and yield the most substantially increases, and improves production efficiency.
Embodiment 4:
By VCM 18 tons, peroxidating diethoxy ethyl ester 5.5kg, azodiisobutyronitrile 4.5Kg, desalted water 20 tons, ten
Dialkyl benzene sulfonic acids sodium 150Kg, octadecyl alcolol 200Kg；Add in premix groove, through 4.5kw/m3Power stirs, and adds the two of series connection
Platform mulser emulsifies, and adds in polymeric kettle, carries out polymerisation in 48 cubic metres of polymerization reaction kettles, polymerization temperature 45 DEG C, when
When reaction proceeds to 60min, jacket of polymerization and stirring cooling water inflow are respectively 202 m3/ h and 68m3/ h, imports and exports water temperature
Being respectively 22.6 DEG C and 24.3 DEG C, trying to achieve rate of heat release is:
Q=WC (T2-T1)=(202+68) × 1000 × 4.2(24.3-22.6)/60=32130kj/ divides
Monomer speed should be the most greatly:
DW=Q × (1-d/1400)/1600=32130(1-862/1400)/1600=7.71kg/ divides
Starting monomer feed pump 1, add VCM 860 minutes with the speed that 6.8kg/ divides, total amount about 5800kg, during polymerization
Between be 1192 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing to reclaim, forcing recovery to add simultaneously
Entering thinner, still pressure is recycled to-0.05mpa, and recovery terminates, and carries out discharging.
Latex spray dryer is the most size-reduced and obtains finished product 21720kg, its volume average particle size 4.026 μm,
Span 2.545, average degree of polymerization 1671.
Embodiment 5:
By VCM 18 tons, peroxy dicarbonate di-n-propyl ester 5.5kg, ABVN 4.5Kg, desalted water 20 tons,
Lauryl sodium sulfate 150Kg, hexadecanol 200Kg；Add in premix groove, through 4.5kw/m3Power stirs, and adds the two of series connection
Platform mulser emulsifies, and adds in polymeric kettle, carries out polymerisation in 48 cubic metres of polymerization reaction kettles, polymerization temperature 45 DEG C, when
When reaction proceeds to 30min, jacket of polymerization and stirring cooling water inflow are respectively 190 and 63m3/h, import and export water temperature and are respectively
23 DEG C and 24.6 DEG C, trying to achieve rate of heat release is:
Q=WC (T2-T1)=(190+63) × 1000 × 4.2(24.6-23)/60=28336kj/ divides
Monomer speed should be the most greatly:
DW=Q × (1-d/1400)/1600=28336(1-862/1400)/1600=6.80kg/ divides
Start monomer feed pump 1, add VCM 980 minutes with the speed that 5kg/ divides, total amount about 4900kg, polymerization time
It it is 1216 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing to reclaim, forcing recovery to be simultaneously introduced
Thinner, still pressure is recycled to-0.05mpa, and recovery terminates, and carries out discharging.
Latex spray dryer is the most size-reduced and obtains finished product 21640kg, its volume average particle size 3.876 μm,
Span 2.335, average degree of polymerization 1705.
Embodiment 6
By VCM 18.5 tons, di-isopropyl peroxydicarbonate 5.5kg, azodiisobutyronitrile 4.5Kg, desalted water 20
Ton, potassium oleate 150Kg, stearic acid 200Kg；Add in premix groove 2, through 4.5kw/m3Power stirs, and adds two breasts of series connection
Change machine emulsifies, and adds in polymerization reaction kettle 6, carries out polymerisation in 48 cubic metres of polymerization reaction kettles 6, polymerization temperature 45 DEG C,
When reaction proceeds to 50min, polymerization reaction kettle 6 chuck and stirring cooling water inflow are respectively 185 m3/ h and 61m3/ h, imports and exports
Water temperature is respectively 23.3 DEG C and 24.8 DEG C, tries to achieve rate of heat release and is:
Q=WC (T2-T1)=(185+61) × 1000 × 4.2(24.8-23.3)/60=25410kj/ divides
Maximum adds VCM speed and should be:
DW=Q × (1-d/1400)/1600=25410(1-862/1400)/1600=6.10kg/ divides
Start monomer feed pump 1, add VCM 1000 minutes with the speed that 4.5kg/ divides, total amount about 4500kg, polymerization
Time is 1108 minutes.Reaction pressure judges to terminate after declining 0.2 Mpa, carries out, from pressing and forcing to reclaim, forcing to reclaim simultaneously
Adding thinner, still pressure is recycled to-0.05mpa, and recovery terminates, and carries out discharging.
Latex spray dryer is the most size-reduced and obtains finished product 22140kg, its volume average particle size 3.167 μm,
Span 2.607, average degree of polymerization 1697.
Claims (10)
1. the method improving micro suspension PVC paste resin production efficiency, is carried out as follows: by initiator, emulsification
Add polymeric kettle after agent, assistant for emulsifying agent, VCM and desalted water emulsification, react at 40 DEG C～60 DEG C, react beginning 30
After 60 minutes, add VCM.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 1, it is characterised in that: draw
Send out agent, emulsifying agent, assistant for emulsifying agent, VCM and these five kinds of materials of desalted water and carry out proportioning by following quality: initiator accounts for
The 0.01～0.3% of VCM quality, emulsifying agent accounts for the 0.2～0.8% of VCM quality；Assistant for emulsifying agent accounts for vinyl chloride
The 1.0～2.5% of monomer weight；Soft water accounts for the 100～105% of VCM weight.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 1, it is characterised in that: draw
Send out agent for including peroxide such as α, α '-bis-(neodecanoic acid) diisopropylbenzyl ester, peroxidating neodecanoic acid cumyl ester, peroxidating two carbon
Acid di-n-propyl ester, peroxy dicarbonate two (2-2 epoxide second fat), di-isopropyl peroxydicarbonate, peroxidating neodecanoic acid 1,1,
3,3-tetramethyl butyl ester, peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxidating neodecanoic acid 1-cyclohexyl-1 methyl second
Ester, peroxy dicarbonate two-2 ethoxy ethyl ester, peroxy dicarbonate two-2 Octyl Nitrite, the tertiary own ester of peroxidating neodecanoic acid, mistake
Aoxidize two carbonic acid dimethoxy butyl esters, peroxy dicarbonate two (3-methyl-3 methoxybutyl) ester, the tertiary fourth of peroxidating neodecanoic acid
Ester, the peroxidating tertiary own ester of neopentanoic acid etc. and azo compound；Initiator；Be single one can also be that two or more are multiple
With.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 1, it is characterised in that: breast
Agent be neopelex, lauryl sodium sulfate, potassium oleate, N-cetyl N ethyl morpholine ethanol base ammonium sulfate,
Polyoxyethylene monostearate or octylphenol ether, kind therein or several.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 1, it is characterised in that: help
Emulsifying agent be hexadecanol, octadecyl alcolol or stearic acid therein one or more.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 1, it is characterised in that: will
Initiator, emulsifying agent, assistant for emulsifying agent, VCM and desalted water are thoroughly mixed in airtight mixing channel, stir merit
Rate 2～5kw/m3, after carrying out mixing operation emulsification in mulser, react in adding reactor.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 6, it is characterised in that: will
Material after the mixing homogenizer of two series connection emulsifies, and the material after mixing initially enters First emulsification
Machine emulsifies, and the material after First mulser emulsifies enters second mulser and emulsifies, is subsequently adding reaction
Still carries out polymerisation.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 1, it is characterised in that: anti-
After should starting, add VCM with following speed:
In formula: dW adds monomer speed kg/ and divides；The heat kj/ of Q reactor removal divides；VCM under d reaction temperature
Density kg/m3；The 1600 hot kj/kg of polymerization of vinyl choride monomer；Density kg/m of 1400 polyvinyl chloride3。
9., according to the method for the raising micro suspension PVC paste resin production efficiency described in claim 1 or 8, its feature exists
In: the amount adding VCM is to account for initial reaction stage to add the 5～30w/% of quality.
The method of raising micro suspension PVC paste resin production efficiency the most according to claim 2, it is characterised in that:
Emulsifying agent accounts for VCM quality 0.3～0.5%；Assistant for emulsifying agent accounts for the 1.5～2.0% of VCM weight；Initiator is used
Amount is the 0.04～0.10w/% of VCM quality.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
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| 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 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952229A (en) * | 2011-08-26 | 2013-03-06 | 沈阳化工股份有限公司 | PVC (Polyvinyl Chloride) paste resin and preparation method thereof |
| CN103709286A (en) * | 2013-10-17 | 2014-04-09 | 天津渤天化工有限责任公司 | Method using nontoxic initiator for preparation of PVC (polyvinyl chloride) paste resin |
| CN104072649A (en) * | 2014-06-27 | 2014-10-01 | 唐山三友氯碱有限责任公司 | Method for producing polyvinyl chloride paste resin |
| CN104530275A (en) * | 2014-12-31 | 2015-04-22 | 安徽天辰化工股份有限公司 | Low-viscosity high-foaming type polyvinyl chloride paste resin PB110-3 and production method thereof |
-
2016
- 2016-06-29 CN CN201610492338.2A patent/CN105884945B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952229A (en) * | 2011-08-26 | 2013-03-06 | 沈阳化工股份有限公司 | PVC (Polyvinyl Chloride) paste resin and preparation method thereof |
| CN103709286A (en) * | 2013-10-17 | 2014-04-09 | 天津渤天化工有限责任公司 | Method using nontoxic initiator for preparation of PVC (polyvinyl chloride) paste resin |
| CN104072649A (en) * | 2014-06-27 | 2014-10-01 | 唐山三友氯碱有限责任公司 | Method for producing polyvinyl chloride paste resin |
| CN104530275A (en) * | 2014-12-31 | 2015-04-22 | 安徽天辰化工股份有限公司 | Low-viscosity high-foaming type polyvinyl chloride paste resin PB110-3 and production method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN116355488A (en) * | 2022-12-02 | 2023-06-30 | 鄂尔多斯市瀚博科技有限公司 | Continuous flow production process of anti-sticking kettle agent |
| 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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