CN1576310A - Method and apparatus for producing pulp - Google Patents
Method and apparatus for producing pulp Download PDFInfo
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- CN1576310A CN1576310A CN 200410070981 CN200410070981A CN1576310A CN 1576310 A CN1576310 A CN 1576310A CN 200410070981 CN200410070981 CN 200410070981 CN 200410070981 A CN200410070981 A CN 200410070981A CN 1576310 A CN1576310 A CN 1576310A
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Abstract
The invention provides a method for producing a syrup while suppressing the runaway reaction even in the unintentional stop of utility supply to prevent the damage of the reactor and provide an apparatus for the production of syrup.A syrup having a polymer content of 1-40% is produced by partly polymerizing a methyl methacrylate monomer in a reactor while boiling the monomer under atmospheric pressure. A condenser satisfying formula (1): CW*W*Hr<Q*100 and formula (2): CW*W*Hr<2.1*10<4>*S is placed in the vapor phase or at the outside directly connected to the vapor phase and the evaporated monomer is condensed with the condenser and returned to the reaction liquid. In the formulas, CW is the polymer conversion (=0.01 to 0.4), W is the charged amount (kg) of the monomer, Hr is heat of reaction (kJ/kg) of the monomer, Q is the heat capacity (kJ/[deg.]C) of the condenser and S is the condensing area (m<2>) of the condenser. The production apparatus is furnished with the condenser.
Description
Technical field
The present invention is a kind of about being resin board in order to make methyl methacrylate by the cast molding polymerization for example, is used to cast with the manufacture method and the manufacturing installation of the useful slurry of slurry.
Background technology
By methyl methacrylate or the methyl methacrylate system slurry that constitutes as the partial polymer of the monomer mixture of main component with methyl methacrylate, with slurry, the method that obtains moulded product is used injecting that various models make its polymerization as casting.As making the method that this methyl methacrylate is a slurry, for example known, special public clear 56-44086 communique, the methyl methacrylate of packing in reaction vessel is a monomer, after being heated to the temperature of regulation, drop into polymerization starter, carry out partially polymerized intermittent type manufacture method at a certain temperature.
When adopting prior art to make methyl methacrylate system slurry, make the monomer condensation of having evaporated, it is necessary being back in the reaction solution again.Because if do not make the monomers flow back of having evaporated, then because evaporation concentrates reaction solution, because of uncontrolled reaction takes place gel effect, the reaction solution between instantaneous in the reactor solidifies.Therefore, in the prior art, the monomeric condensation that cooling water circulation grade has been evaporated with recycle pump.
Summary of the invention
If it is in the condensation of having evaporated, supply with necessary useful matter (water coolant, cooling water circulating pump electric etc.), no problem usually.But, owing under the situation that the supply of useful matteies such as power failure is stopped, then have problems.In the prior art, especially do not have to disclose about controlling the method and apparatus of the uncontrolled reaction under the situation like this.In general, stopping of useful matter is recurrent in industrial equipments.The inventor is conceived to such problem, has studied its treatment process.If effective treatment process can be provided, it will become industrial very significant treatment process.
Promptly the object of the present invention is to provide, in the manufacturing of slurry, even owing to have a power failure to wait under the situation of the supply that stops useful matter, control uncontrolled reaction, the manufacture method and the manufacturing installation of the slurry that reactor is not damaged.
The present invention is the manufacture method of slurry, in reactor, under atmospheric pressure, make on one side methyl methacrylate separately or make contain 20 quality % or its following can be the monomer mixture boiling with the methyl methacrylate of at least a unsaturated ethylene alkenyl compound of its copolymerization, polymerization on one side is a part wherein, making the polymkeric substance containing ratio is the method for the slurry of 1～40 quality %, it is characterized in that, the condenser arrangement of condensation area that has the thermal capacity that satisfies following formula (1) and satisfy following formula (2) in this reactor gas phase portion or with the direct-connected outside of gas phase portion, make the monomer condensation of having evaporated by this condenser, this phlegma is turned back in the reaction solution.
CW×W×Hr＜Q×100?????????(1)
CW×W×Hr＜2.1×10
4×S????(2)
CW: as the polymkeric substance transformation efficiency [-] (=0.01～0.4) of purpose
W: the Intake Quantity of the monomer mixture in the reactor [kg]
Hr: methyl methacrylate separately or the reaction heat [kJ/kg] of monomer mixture
Q: the thermal capacity of condenser [kJ/ ℃]
S: the condensation area [m of condenser
2]
The present invention is again the manufacturing installation of slurry, in reactor, under atmospheric pressure, make on one side methyl methacrylate separately or make contain 20 quality % or its following can be the monomer mixture boiling with the methyl methacrylate of at least a unsaturated ethylene alkenyl compound of its copolymerization, polymerization on one side is a part wherein, making the polymkeric substance containing ratio is the device of the slurry of 1～40 quality %, it is characterized in that, the condenser arrangement of condensation area that has the thermal capacity that satisfies above-mentioned formula (1) and satisfy above-mentioned formula (2) in this reactor gas phase portion or with the direct-connected outside of gas phase portion, have by this condenser and make the phlegma of condensation turn back to the structure of reactor.
About the present invention, because the thermal capacity of condenser satisfies the relation of above-mentioned formula (1), therefore, even stop to feed under the situation of water coolant owing to power failure waits, before reaction finished, the temperature of condenser can not surpass monomeric boiling point yet.In addition, because the condensation area of condenser satisfies the relation of above-mentioned formula (2), thereby monomeric relatively velocity of evaporation can obtain being enough to make the rate of heat exchange of its condensation.Therefore,, also can suppress uncontrolled reaction, reactor is not caused damage even in the manufacturing of slurry, wait under the situation of the supply that stops useful matter owing to having a power failure.Manufacture method and manufacturing installation with slurry of such advantage, industrial be very useful.
Embodiment
The monomer of Shi Yonging in the present invention, be methyl methacrylate separately or to contain at least a can be monomer mixture with the methyl methacrylate of the unsaturated ethylene alkenyl compound of its copolymerization.Methyl methacrylate is that monomer mixture contains 80 quality % or its above methyl methacrylate.As can with the unsaturated ethylene alkenyl compound of methyl methacrylate copolymer, for example can enumerate the methacrylic ester beyond the methyl methacrylates such as Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, methacrylic acid 2-ethylhexyl, benzyl methacrylate; Acrylate such as methyl acrylate, ethyl propenoate, butyl acrylate, cyclohexyl acrylate, 2-EHA, benzyl acrylate; Vinylbenzene, alpha-methyl styrene etc.
As for the polymerization methyl methacrylate separately or contain at least a can be with the methyl methacrylate of the unsaturated ethylene alkenyl compound of its copolymerization monomer mixture (below, it is generically and collectively referred to as " methyl methacrylate is a monomer ") and the polymerization starter of use for example can be enumerated organo-peroxides such as two carbonic acid diisopropyl esters, the neodecanoic acid tert-butyl ester, t-butylperoxy pivarate, lauric acid superoxide, benzoyl peroxide, the peroxy isopropyl base carbonic acid tert-butyl ester, t-butyl per(oxy)benzoate, dicumyl peroxide, ditertiary butyl peroxide; 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azobis isobutyronitrile, dimethyl 2,2 '-azo two (propionic acid 2-methyl esters), 2,2 '-the two azo-compounds such as (2-methylbutyronitriles) of azo.
The addition of polymerization starter, monomeric total amount in the reactor of packing into relatively usually is preferably about 0.01～0.5 quality %.Especially, preferably decide suitable addition according to polymkeric substance transformation efficiency as purpose.In addition, molecular weight regulator can be used, also molecular weight regulator can be do not used.As molecular weight regulator, preferably have alkyl or substituted alkyl primary, the second month in a season or uncle's mercaptan.As such mercaptan, for example can enumerate normal-butyl mercaptan, isobutyl-mercaptan, tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, sec-butyl mercaptan, secondary lauryl mercaptan etc.
Methyl methacrylate in the reactor is a monomer, removes dissolved oxygen fully before being preferably in polymerization and beginning.Especially, this dissolved oxygen concentration 1ppm or below it preferably.As the method for removing dissolved oxygen, can use known so far the whole bag of tricks.For example, can enumerate and carry out nitrogen froth in monomer, the method for the degassing etc. perhaps reduces pressure.Input polymerization starter when being preferably in the heating monomer and reaching some in 60 ℃～90 ℃.After polymerization starter drops into, give birth to heat and automatically reach boiling point owing to polymerization usually, and be maintained at certain temperature.
The present invention in reactor, under atmospheric pressure, is the monomer boiling Yi Bian make methyl methacrylate, Yi Bian make one partially polymerized.Owing to make to reach normal atmosphere in the reactor, carry out polyreaction at boiling point, so in the control of polymerization temperature, become favourable.The boiling point of methyl methacrylate monomer under atmospheric pressure is 100～102 ℃.In addition, though contain 20 quality % or below it other can copolymerization the situation of unsaturated ethylene alkenyl compound under, boiling point is also probably near 100～102 ℃.Keep in the reactor under atmospheric pressure in order to make, for example atmospheric pressure opening port is led in the setting of gas phase portion in still, is preferably in the polyreaction open in advance.
Polymerization time is relevant with polymerization temperature, the transformation period under the polymerization temperature of polymerization starter, the usage quantity of polymerization starter etc., usually, from polymerization begin to the refrigerative time be about 5～30 minutes.After finishing this polyreaction, proceed cooling usually.In this process of cooling, in order to make the slurry of not following inappropriate viscosity to rise greatly, during the cooling beginning, the amount of remaining polymerization starter in the slurry preferably for the viscosity that does not make slurry becomes greatly irrelevantly, and makes it become lower concentration.Especially, remaining initiator concentration 5ppm or below it preferably.
The present invention utilizes the gas phase portion be configured in the reactor or makes because of polymerization with the condenser of gas phase portion direct-connected outside and gives birth to the monomer condensation that heat evaporate, and it is back in the interior reaction solution of reactor (in the slurry).Therefore, can prevent the concentrated uncontrolled reaction that causes by reaction solution.Quantity of reflux, the monomer total amount of relatively having evaporated, preferred 90 quality % or more than it.Preferred especially 95 quality % or more than it.In addition,, stirrer is set in reactor, preferably under agitation reacts in order to mix phegma and reaction solution well.
Device as used herein, preferentially select condenser arrangement in reactor gas phase portion or with gas phase portion direct-connected outside, have the phlegma that makes by this condenser condenses and turn back to structure in the reactor, just so-called intermittent reaction device.As condenser, use the condenser that has the thermal capacity that satisfies following formula (1) and satisfy the condensation area of following formula (2).
CW×W×Hr＜Q×100?????????(1)
CW×W×Hr＜2.1×10
4×S????(2)
CW: as the polymkeric substance transformation efficiency [-] (=0.01～0.4) of purpose
W: the Intake Quantity of the monomer mixture in the reactor [kg]
Hr: methyl methacrylate separately or the reaction heat [kJ/kg] of monomer mixture
Q: the thermal capacity of condenser [kJ/ ℃]
S: the condensation area [m of condenser
2]
About the reaction heat Hr in the above-mentioned rerum natura, the independent polymerization reaction heat of methyl methacrylate is 544.3kJ/kg.In addition, when the methyl methacrylate that contains the unsaturated ethylene alkenyl compound of methyl methacrylate and other in use is monomer mixture, owing to contain 80 quality % or its above methyl methacrylate, so its reaction heat Hr also is approximately 544.3kJ/kg.In addition, the thermal capacity Q of condenser adds up to the thermal capacity burden part of the thermal capacity of employed condenser self and the water that uses in condenser, and the whole thermal capacity when using this condenser are as Q.
Owing to use the condenser that satisfies formula (1) and formula (2), even wait under the situation of the supply that stops useful matter because of having a power failure, when the water coolant that common use is about 10 ℃ led to liquid, only the thermal capacity that keeps with condenser also can make monomeric 90 quality % or its above condensation of having evaporated.Therefore, can inhibited reaction liquid concentrate can prevent solidifying, damaging of reactor.
Especially, if the thermal capacity of condenser in the scope of formula (1), even then owing to stopping to feed under the situation of water coolant, the temperature of condenser can not surpass monomeric boiling point yet before reaction finishes.Therefore, the monomer that takes place hardly to have evaporated is discharged to the system outside of reactor under uncondensable situation.Therefore, can prevent the uncontrolled reaction that causes by concentrating of reaction solution.And then the thermal capacity of condenser preferably satisfies following formula (1 ').
CW×W×Hr＜Q×80??????????(1′)
In addition, if the condensation area of condenser in the scope of formula (2), then monomeric relatively velocity of evaporation can access the rate of heat exchange that is enough to make monomer condensation.Therefore, the monomer that takes place hardly to have evaporated is discharged to the system outside of reactor under uncondensable situation.Therefore, can prevent the uncontrolled reaction that causes by concentrating of reaction solution.And then the condensation area of condenser preferably satisfies following formula (2 ').
CW×W×Hr＜1.6×10
4×S????(2′)
As the object lesson of condenser, can enumerate the plate cooler that is installed in the gas phase portion in the reactor, the multi tube heat exchanger of backflow usefulness etc. perhaps is set between atmosphere opening is with nozzle and the close water cooler of atmosphere opening portion.But, being not limited to this, the coil pipe type coil pipe etc. that for example feeds water coolant in inside also can be used as condenser and uses.
In the present invention, by the part of the reaction solution in the polymerization reaction kettle (monomer), can obtain methyl methacrylate system slurry.The polymkeric substance containing ratio of this slurry is 1～40 quality %.This polymkeric substance containing ratio is if 1 quality % or more than it, and the viscosity of slurry just can not be low excessively, can use with slurry as casting well.From this viewpoint, preferred especially 5 quality % of polymkeric substance containing ratio or more than it.In addition, the polymkeric substance containing ratio is if 40 quality % or below it, and viscosity just can not be too high, is difficult for taking place the out of control of the polyreaction that caused by gel effect in polyreaction, and it is easy that the control of reaction becomes.From this viewpoint, the polymkeric substance containing ratio is more preferably 30 quality % or below it.In addition, as the suitable viscosity of casting, be 0.2～4.0Pas at 25 ℃ with slurry.
This slurry for example after polyreaction, then is cooled to about 70 ℃, can take out from reactor.As this method of cooling, for example the cannula portion that can enumerate at reactor flows through cold water, and utilizing conducts heat carries out the refrigerative method, perhaps makes in the reactor after polyreaction finishes and reduces pressure, and utilizes monomeric vaporization heat to carry out refrigerative method etc.But, not necessarily must be these method of cooling.And, take out the slurry that obtains from reactor, can be cooled to room temperature storage.As the method that is cooled to normal temperature, just being received in the storage tank the heat exchanger logical liquid refrigerative method that circulates in case can enumerate, perhaps to the pipe arrangement way that storage tank is carried, utilizing the method that is cooled to normal temperature by heat exchanger, with single passage etc. from reactor.But, not necessarily must be these method of cooling.In addition, before taking out, in slurry, can add stopper from reactor.
According to the slurry that the present invention obtains, for example the polymerizability raw material (casting slip) as cast molding is very useful, can be applicable to inject that various moulds make its polymerization and the method that obtains moulded product.Be particularly preferred for the manufacturing of methyl-methacrylate resin plate.In addition, this slurry can also add uses such as dye pigment, the stablizer to light and heat, releasing agent, softening agent, lubricant, linking agent, glass fibre, inorganic filler as required.These additives can be added on later on after the polymerization in the chilled slurry, also can be added in advance in the monomer before the polymerization.
Below, illustrate in greater detail the present invention by embodiment.
Embodiment 1-1
Gas phase portion in the reactor of being made by material SUS304, as condenser, the installation material is that SUS304, condensation area are 0.06m
2Plate cooler.The monomeric weight of plate cooler is 4.4kg, and the volume of the water in this plate cooler is 1.33 liters (being 1.33kg).Be equipped with sleeve pipe in the side chamber of reactor portion, accomplishing can enough steam heating.In addition, form normal atmosphere in the reactor in order to make, portion is provided with nozzle in gas phase, and atmosphere opening is carried out at the tip of nozzle.In order to measure outside system the amount of monomer of discharging, in this side water cooler is set near the atmosphere opening portion of this nozzle, capture phlegma.Stirrer also is set in reactor.
In this reactor, the 5000g methyl methacrylate of packing into carries out 10 minutes nitrogen and froths.Dissolved oxygen concentration after nitrogen froths is 0.2ppm.Then, in plate cooler, feed 10 ℃ cold water, the monomer in the stirred autoclave of limit, the limit feeds steam in cannula portion, and monomer is heated to 80 ℃, drops into 3.25g azo two (2, the 4-methyl pentane nitrile) as polymerization starter.Dropping into this polymerization starter simultaneously, stop the steam of cannula portion.Reacting liquid temperature continues to rise, and shows 101 ℃ after 1 minute, makes this temperature maintenance 7 minutes while seethe with excitement.After this, make decompression in the reactor, after the temperature of reaction solution is cooled to 70 ℃, be fetched into the storage tank, be cooled to normal temperature, just obtain methyl methacrylate system slurry from reactor.The polymkeric substance containing ratio of this slurry is 20 quality %, and the viscosity in the time of 25 ℃ is 2.0Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 10g.
Embodiment 1-2
Except in embodiment 1-1, when dropping into polymerization starter, stop beyond plate cooler feeds water coolant and stirs, with identical method manufacturing slurry.After dropping into polymerization starter, reacting liquid temperature continues to rise, and shows 101 ℃ after 1 minute, makes this temperature maintenance 8 minutes while seethe with excitement.After this, when the temperature of reaction solution drops to 90 ℃, be fetched into the storage tank, be cooled to normal temperature, just obtain methyl methacrylate system slurry from reactor.The polymkeric substance containing ratio of this slurry is 25 quality %, and the viscosity in the time of 25 ℃ is 3.0Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 100g.Present embodiment is compared with embodiment 1-1, though the polymkeric substance containing ratio of slurry uprises a little, uncontrolled reaction does not take place, can take out slurry safely.
Embodiment 2-1
In embodiment 1-1, using the methyl methacrylate that is made of 4900g (98.0 quality %) methyl methacrylate and 100g (2.0 quality %) n-butyl acrylate as monomer is monomer mixture, drop into 5.0g azo two (2 as polymerization starter, the 4-methyl pentane nitrile), and as chain mobile agent input 2.0g n-dodecyl mercaptan, in addition, with identical method manufacturing slurry.The polymkeric substance containing ratio of this slurry is 27 quality %, and the viscosity in the time of 25 ℃ is 2.0Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 12g.
Embodiment 2-2
Except in embodiment 2-1, when dropping into polymerization starter, stop beyond plate cooler feeds water coolant and stirs, with identical method manufacturing slurry.After dropping into polymerization starter, reacting liquid temperature continues to rise, and shows 101 ℃ after 1 minute, makes this temperature maintenance 8 minutes while seethe with excitement.After this, when the temperature of reaction solution drops to 90 ℃, be fetched into the storage tank, be cooled to normal temperature, just obtain methyl methacrylate system slurry from reactor.The polymkeric substance containing ratio of this slurry is 32 quality %, and the viscosity in the time of 25 ℃ is 5.5Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 130g.Present embodiment is compared with embodiment 2-1, though the polymkeric substance containing ratio of slurry uprises a little, uncontrolled reaction does not take place, can take out slurry safely.
Embodiment 3-1
In embodiment 1-1, remove the plate cooler that is arranged on the gas phase portion in the reactor, instead of the nozzle of using at atmosphere opening with near the multi tube heat exchanger that backflow usefulness is set between the water cooler of atmosphere opening portion, the monomer that cooling has been evaporated accomplishes that phegma returns in the reactor.The material of this multi tube heat exchanger is SUS304, and condensation area reaches 0.06m
2In addition, the monomeric weight of multi tube heat exchanger is 4.9kg, and the volume of the water in the multi tube heat exchanger is 1.47 liters (being 1.47kg).Except using the device of gas phase portion in this reactor, with the method manufacturing slurry identical with embodiment 1-1 as the multi tube heat exchanger (feeding 10 ℃ of cold water) of condenser setting.The polymkeric substance containing ratio of this slurry is 20 quality %, and the viscosity in the time of 25 ℃ is 2.0Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 5g.
Embodiment 3-2
Except in embodiment 3-1, in the input of polymerization starter, stop beyond multi tube heat exchanger feeds water coolant and stirs, with identical method manufacturing slurry.After dropping into polymerization starter, reacting liquid temperature continues to rise, and shows 101 ℃ after 1 minute, makes this temperature maintenance 8 minutes while seethe with excitement.After this, when the temperature of reaction solution drops to 90 ℃, be fetched into the storage tank, be cooled to normal temperature, just obtain methyl methacrylate system slurry from reactor.The polymkeric substance containing ratio of this slurry is 24 quality %, and the viscosity in the time of 25 ℃ is 2.8Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 80g.Present embodiment is compared with embodiment 3-1, though the polymkeric substance containing ratio of slurry uprises a little, uncontrolled reaction does not take place, can take out slurry safely.
Comparative example 1-1
It is that SUS304, condensation area are 0.06m that the plate cooler that will use in embodiment 1-1 replaces to material
2Identical, be the plate cooler of 0.33 liter (being 0.33kg) but monomer weight is the volume of 1.1kg, water.Except using this plate cooler, with the method manufacturing slurry identical with embodiment 1-1.The polymkeric substance containing ratio of this slurry is 20 quality %, and the viscosity in the time of 25 ℃ is 2.0Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 10g.
Comparative example 1-2
Except in comparative example 1-1, when dropping into polymerization starter, stop beyond plate cooler feeds water coolant and stirs, with identical method manufacturing slurry.After dropping into polymerization starter, reacting liquid temperature continues to rise, and shows 101 ℃ after 1 minute, keeps this temperature while seethe with excitement, but after 10 minutes, in the same old way owing to uncontrolled reaction is solidified.In addition, the amount of monomer that captures in atmosphere opening portion is 1500g.
Comparative example 2-1
It is that SUS304, condensation area are 0.06m that the multi tube heat exchanger that will use in embodiment 3-1 replaces to material
2Identical, be the multi tube heat exchanger of 0.40 liter (being 0.40kg) but monomer weight is the volume of 1.3kg, water.Except using this multi tube heat exchanger, with the method manufacturing slurry identical with embodiment 3-1.The polymkeric substance containing ratio of this slurry is 20 quality %, and the viscosity in the time of 25 ℃ is 2.0Pas.In addition, the amount of monomer that captures in atmosphere opening portion is 10g.
Comparative example 2-2
Except in comparative example 2-1, when dropping into polymerization starter, stop beyond multi tube heat exchanger feeds water coolant and stirs, with identical method manufacturing slurry.After dropping into polymerization starter, reacting liquid temperature continues to rise, and shows 101 ℃ after 1 minute, keeps this temperature while seethe with excitement, but after 10 minutes, in the same old way owing to uncontrolled reaction is solidified.In addition, the amount of monomer that captures in atmosphere opening portion is 1500g.
Comparative example 3
It is identical with SUS304 that the plate cooler that will use in embodiment 1-1 replaces to material, but condensation area is 0.01m
2, monomer weight is that the volume of 1.3kg, water is the plate cooler of 1.8 liters (they being 1.8kg).Except using this plate cooler, with the method manufacturing slurry identical with embodiment 1-1.But although feed water coolant in plate cooler, viscosity rises to the state that can not stir after 7 minutes, uncontrolled reaction takes place and reaches and solidifies.In addition, the amount of monomer that captures in atmosphere opening portion is 1000g.
In following table 1, about each above embodiment and each comparative example, put down in writing create conditions, the Intake Quantity W[kg of the monomer mixture in the reactor], methyl methacrylate separately or the reaction heat Hr[kJ/kg of monomer mixture], as the polymkeric substance transformation efficiency CW of the slurry of purpose etc.In addition, in these conditions, also put down in writing in order to satisfy formula (1) and formula (2) thermal capacity Q[kJ/ ℃ of the condenser in the necessary calculating] and condensation area S[m
2] and thermal capacity Q[kJ/ ℃ of the actual condenser that in embodiment and comparative example, uses] and condensation area S[m
2], also gather the evaluation of having put down in writing polymerization movement etc.Moreover, the physics value that uses during the thermal capacity of condenser is in an embodiment calculated, the specific heat of SUS304 is 0.628kJ/ (kg ℃), specific heat of water is 4.187kJ/ (kg a ℃).
Table 1
| Intake Quantity W | Amount of monomer is formed | Reaction heat Hr | Polymkeric substance transformation efficiency CW | Condenser size | The necessary thermal capacity Q value of formula (1) | The thermal capacity of employed condenser is calculated | The necessary condensation area S value of formula (2) | The condensation area S of employed condenser | The type of cooling | The logical liquid operation of water coolant | The polymerization movement | ||||
| The SUS304 quality | Quality | The thermal capacity Q that condenser is all | The monomeric thermal capacity of condenser | Thermal capacity burden part of water | |||||||||||
| ?[kg] | [quality %] | ??[kJ/kg] | ????[-] | ???[kg] | ??[kg] | ??[kJ/℃] | ????[kJ/℃] | ???[kJ/℃] | ???[kJ/℃] | ????[m 2] | ???[m 2] | ||||
| Embodiment 1-1 | ??5 | ??MMA100 | ???544.3 | ???0.2 | ???4.4 | ??1.33 | ???5.44 | ?????8.33 | ?????2.76 | ????5.57 | ????0.026 | ????0.06 | Inner plate cooler | Long-time logical liquid | Polymerization-stable |
| Embodiment 1-2 | ??↑ | ??↑ | ???↑ | ???↑ | ???↑ | ??↑ | ???↑ | ?????↑ | ?????↑ | ????↑ | ????↑ | ????↑ | ????↑ | Stop water coolant in the time of the polymerization starter input | Polymerization-stable |
| Embodiment 2-1 | ??5 | ??MMA98 ??BA?2 | ???544.3 | ???0.27 | ???4.4 | ??1.33 | ???7.35 | ?????8.33 | ?????2.76 | ????5.57 | ????0.035 | ????0.06 | Inner plate cooler | Long-time logical liquid | Copolymerization is stable |
| Embodiment 2-2 | ??↑ | ??↑ | ???↑ | ???↑ | ???↑ | ??↑ | ???↑ | ?????↑ | ?????↑ | ????↑ | ????↑ | ????↑ | ????↑ | Stop water coolant in the time of the polymerization starter input | Copolymerization is stable |
| Embodiment 3-1 | ??5 | ??MMA100 | ???544.3 | ???0.2 | ???4.9 | ??1.47 | ???5.44 | ?????9.23 | ?????3.08 | ????6.15 | ????0.026 | ????0.06 | Outside multi-tubular heat exchanger | Long-time logical liquid | Polymerization-stable |
| Embodiment 3-2 | ??↑ | ??↑ | ???↑ | ???↑ | ???↑ | ??↑ | ???↑ | ?????↑ | ?????↑ | ????↑ | ????↑ | ????↑ | ????↑ | Stop water coolant in the time of the polymerization starter input | Polymerization-stable |
| Comparative example 1-1 | ??5 | ??MMA100 | ???544.3 | ???0.2 | ???1.1 | ??0.33 | ???5.44 | ?????2.07 | ?????0.69 | ????1.38 | ????0.026 | ????0.06 | Inner plate cooler | Long-time logical liquid | Polymerization-stable |
| Comparative example 1-2 | ??↑ | ??↑ | ???↑ | ???↑ | ???↑ | ??↑ | ???↑ | ?????↑ | ?????↑ | ????↑ | ????↑ | ????↑ | ????↑ | Stop water coolant in the time of the polymerization starter input | Out of control |
| Comparative example 2-1 | ??5 | ??MMA100 | ???544.3 | ???0.2 | ???1.3 | ??0.4 | ???5.44 | ?????2.49 | ?????0.82 | ????1.67 | ????0.026 | ????0.06 | Outside multi-tubular heat exchanger | Long-time logical liquid | Polymerization-stable |
| Comparative example 2-2 | ??↑ | ??↑ | ???↑ | ???↑ | ???↑ | ??↑ | ???↑ | ?????↑ | ?????↑ | ????↑ | ????↑ | ????↑ | ????↑ | Stop water coolant in the time of the polymerization starter input | Out of control |
| Comparative example 3 | ??5 | ??MMA100 | ???544.3 | ???0.2 | ???1.3 | ??1.8 | ???5.44 | ?????8.36 | ?????0.82 | ????7.54 | ????0.026 | ????0.01 | Inner plate cooler | Long-time logical liquid | It is few, out of control to begin condensation number from polymerization |
MMA: methyl methacrylate, BA: n-butyl acrylate
Claims (2)
1. Jiang manufacture method, in reactor, under atmospheric pressure, make on one side methyl methacrylate separately or contain 20 quality % or its following can be the monomer mixture boiling with the methyl methacrylate of at least a unsaturated ethylene alkenyl compound of its copolymerization, polymerization on one side is a part wherein, making the polymkeric substance containing ratio is the method for the slurry of 1～40 quality %, it is characterized in that, the condenser arrangement of condensation area that has the thermal capacity that satisfies following formula (1) and satisfy following formula (2) in this reactor gas phase portion or with the direct-connected outside of gas phase portion, make the monomer condensation of having evaporated by this condenser, this phlegma is returned in the reaction solution
CW×W×Hr＜Q×100??????????(1)
CW×W×Hr＜2.1×10
4×S????(2)
CW: as the polymkeric substance transformation efficiency [-] (=0.01～0.4) of purpose,
W: the Intake Quantity of the monomer mixture in the reactor [kg],
Hr: methyl methacrylate separately or the reaction heat [kJ/kg] of monomer mixture,
Q: the thermal capacity of condenser [kJ/ ℃],
S: the condensation area [m of condenser
2].
2. Jiang manufacturing installation, in reactor, under atmospheric pressure, make on one side methyl methacrylate separately or contain 20 quality % or its following can be the monomer mixture boiling with the methyl methacrylate of at least a unsaturated ethylene alkenyl compound of its copolymerization, polymerization on one side is a part wherein, making the polymkeric substance containing ratio is the manufacturing installation of the slurry of 1～40 quality %, it is characterized in that, the condenser arrangement of condensation area that has the thermal capacity that satisfies following formula (1) and satisfy following formula (2) in this reactor gas phase portion or with the direct-connected outside of gas phase portion, having by this condenser makes the phlegma of condensation turn back to the structure of reactor
CW×W×Hr＜Q×100?????????(1)
CW×W×Hr＜2.1×10
4×S???(2)
CW: as the polymkeric substance transformation efficiency [-] (=0.01～0.4) of purpose,
W: the Intake Quantity of the monomer mixture in the reactor [kg],
Hr: methyl methacrylate separately or the reaction heat [kJ/kg] of monomer mixture,
Q: the thermal capacity of condenser [kJ/ ℃],
S: the condensation area [m of condenser
2].
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| CN107076311A (en) * | 2014-10-22 | 2017-08-18 | Nok株式会社 | Dust cover |
| CN108290162A (en) * | 2015-11-22 | 2018-07-17 | 埃姆斯控股有限责任公司 | Starch lifter |
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| JP2873107B2 (en) * | 1991-03-29 | 1999-03-24 | 三菱レイヨン株式会社 | Method for producing rubber-containing graft copolymer particles |
| JP3628518B2 (en) * | 1998-07-14 | 2005-03-16 | 三菱レイヨン株式会社 | Methacrylic polymer and process for producing the same |
| JP2001270905A (en) * | 2000-01-21 | 2001-10-02 | Mitsubishi Rayon Co Ltd | Heat-resistant methacrylic copolymer, manufacturing method therefor and optical element therefrom |
| JP2002348304A (en) * | 2001-05-29 | 2002-12-04 | Mitsubishi Rayon Co Ltd | Polymerizer and polymerization method |
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| CN107076311A (en) * | 2014-10-22 | 2017-08-18 | Nok株式会社 | Dust cover |
| CN107076311B (en) * | 2014-10-22 | 2018-07-10 | Nok株式会社 | Dust cover |
| CN108290162A (en) * | 2015-11-22 | 2018-07-17 | 埃姆斯控股有限责任公司 | Starch lifter |
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