CN1618820A - Degasifying pressing out device, device and method for mfg. polymer therewith - Google Patents
Degasifying pressing out device, device and method for mfg. polymer therewith Download PDFInfo
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- CN1618820A CN1618820A CN 200410081147 CN200410081147A CN1618820A CN 1618820 A CN1618820 A CN 1618820A CN 200410081147 CN200410081147 CN 200410081147 CN 200410081147 A CN200410081147 A CN 200410081147A CN 1618820 A CN1618820 A CN 1618820A
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Abstract
The present invention provides a manufacturing apparatus and a manufacturing method of a (meth)acrylic polymer where no impurity is interfused, and the polymer desaeration extruding device, wherein, the shaft seal part has no polymer adhered even in a long running term. The polymer desaeration extruding device has an outlet for providing reaction mixture containing polymer and volatilization component, an outlet for discharging the polymer separated from said reaction mixture, one or more outlets capable of discharging said volatilization component separated from said reaction mixture, a rotatable screw and the shaft seal part positioned around the opening having been inserted with the screw for keeping the inner gas tightness, and an air guiding inlet is provided closer to said shaft seal part comparing with any position provided with outlet and the mixture providing outlet. Otherwise, the manufacturing apparatus and the manufacturing method of a (meth)acrylic polymer use the desaeration extruding device.
Description
Technical field
The present invention is, about by successive polymerization manufactured (methyl) acrylic polymers etc. the time, employed degassing extruding device and with the manufacturing installation and the manufacture method of this device, manufacturing (methyl) acrylic polymers.
Background technology
(methyl) acrylic monomer such as polymerization methyl methacrylate and polymethylmethacrylate (methyl) acrylic polymerss such as (PMMA) of making, have the good ground transparency, weathering resistance and good appearance, can be applicable to various fields such as illumination, billboard class and vehicle.Also be widely used in optical lens, disk basal disc, optical applications such as plastic optical fiber.
As the manufacture method of (methyl) acrylic polymers, the general suspension polymerizations that adopt more.But because of used auxiliary agents such as suspension dispersive agent, sneak in (methyl) acronal, and its transparency is descended, thereby be not suitable for optical applications.In addition, owing to miscellaneous operations such as manufacturing processed needs to filter, washs, drying reduce productivity.
As the manufacture method of (methyl) acrylic polymers, except that above-mentioned suspension polymerization, also have methods such as known mass polymerization, solution polymerization.Use these methods, can make (methyl) acrylic polymers that the transparency does not reduce, has good characteristic.And recently noticeablely be to adopt mass polymerization or contain the solution polymerization process of a small amount of solvent, the continuous polymerization of can make continuously, boosting productivity.But when making (methyl) acrylic polymers with these methods, in case this polymkeric substance containing ratio uprises, will produce what is called " gel effect ", and cause the phenomenon that polymerization rate sharply increases, promptly under polymkeric substance containing ratio higher state, be difficult to the polyreaction of control stabilization.
Therefore,, be everlasting the low stage of polymkeric substance containing ratio, finish polyreaction for realizing stable polyreaction.(methyl) acrylic polymers and be reaction mixture major ingredient, the volatilization composition of prepared containing, extract post-heating, pressurization, import and have in the degassing extruding device of outlet then from polymeric kettle with unreacted (methyl) acrylic monomer.In inside be under the decompression state degassing extruding device, remove volatilization composition contained in the reaction mixture, and obtain target compound (methyl) acrylic polymers.For example, known spy opens clear 50-40688 communique, and the reaction mixture obtaining is pressurized to more than or equal to 20kg/cm
2, be heated to 210~270 ℃ after, importing pressure is adjusted to more than or equal to 50torr, smaller or equal to the feed portion of atmospheric degassing extruding device, adjust under the state of adjusting to 250~290 ℃ smaller or equal to 50torr, temperature the manufacture method of volatilization composition poor (methyl) acrylic polymers at the pressure of its export department.
Usually, in degassing extruding device, around the contact part of inner insertion screw rod and degassing extruding device body, form shaft sealing, its structure makes degassing extruding device inside can keep decompression state, and screw rod can be rotated smoothly.But make continuously for a long time, make (methyl) acrylic monomer or its polymkeric substance, the shaft sealing that is deposited in degassing extruding device is paid closely, and has foreign matter to sneak in (methyl) acrylic polymers of manufacturing.Sometimes, even there is polymkeric substance to cover shaft sealing, makes problem generations such as screw rod running difficulty.In addition, during long-term continuous operation, owing to import the change of the reaction mixture pressure of degassing extruding device, the problem that makes near the shaft sealing (methyl) acrylic monomer or its polymkeric substance more be easy to generate accumulation.
Summary of the invention
In view of the foregoing, the objective of the invention is, even long-term operation is provided, do not have polymkeric substance that polymkeric substance makes attached to shaft sealing yet and do not have degassing extruding device that foreign matter sneaks into and can running steady in a long-term and make the manufacturing installation and the manufacture method of (methyl) acrylic polymers that no foreign matter sneaks into.The present invention is a degassing extruding device, it has, and the reaction mixture supplying opening and discharging that can supply with the reaction mixture that contains polymkeric substance and volatilization composition separates from this reaction mixture, the polymkeric substance relief outlet of above-mentioned polymkeric substance and one or several outlets and the revolvable screw rod that can discharge the above-mentioned volatilization composition of separating from this reaction mixture and be arranged at insertion mouth that this screw rod inserts on every side, can keep inner bubble-tight shaft sealing, it is characterized in that, than above-mentioned reaction mixture supplying opening and above-mentioned outlet position is set any compare, the position of more close above-mentioned shaft sealing side further is provided with gas introduction port.Adopt this degassing extruding device, carry out long-term operation and also do not have polymkeric substance, and make the polymkeric substance that no foreign matter is sneaked into attached to axle envelope portion.
Above-mentioned outlet in the above-mentioned degassing extruding device, at least one, preferably be provided with that above-mentioned reaction mixture supplying opening position is compared, the position of more close above-mentioned shaft sealing side is provided with.In addition, more preferably above-mentioned shaft sealing is made of Wilson seal.
Embodiment preferred for this invention is, by being provided with above-mentioned degassing extruding device, polymeric kettle and being connected this polymeric kettle and the manufacturing installation of (methyl) acrylic polymers of the connection section of this degassing extruding device.
Moreover, because above-mentioned connection section is provided with the mechanical type back pressure valve, makes the pressure of the reaction mixture that imports degassing extruding device often keep certain, thereby can prevent fully that polymkeric substance is attached near the shaft sealing.
Embodiment preferred for this invention is characterised in that it adopts above-mentioned degassing extruding device and is provided with
(A) the feedstock composition that contains (methyl) acrylic monomer, free radical polymerization initiator and chain-transfer agent supply with continuously polymeric kettle operation and
(B) in this polymeric kettle, make above-mentioned (methyl) acrylic monomer partially polymerized at least and obtain to contain above-mentioned (methyl) acrylic monomer partially polymerized at least, the operation of the reaction mixture of (methyl) acrylic polymers and
(C) operation that this reaction mixture is extracted from above-mentioned polymeric kettle and
(D) this reaction mixture that extracts from above-mentioned polymeric kettle imports in the above-mentioned degassing extruding device, and from the above-mentioned gas introducing port, the limit imports the processing that outgases of gas, limit, and obtains the manufacture method of (methyl) acrylic polymers of above-mentioned (methyl) acrylic polymers operation.More preferably the gas that imports from the above-mentioned gas introducing port is rare gas element.Being more preferably the gas flow that is imported from the above-mentioned gas introducing port is 0.5~5 liter/minute.
In addition, preferred (methyl) acrylic polymers manufacture method is characterised in that to have by the mechanical type back pressure valve, adjusts the operation of the pressure of the reaction mixture that extracts continuously from above-mentioned polymeric kettle
Adopt degassing extruding device of the present invention, even long-term operation does not have polymkeric substance attached to shaft sealing yet, prepared polymkeric substance can not sneaked into foreign matter, thereby becomes continuous operation for a long time, stably make the manufacturing installation and the manufacture method of (methyl) acrylic polymers that no foreign matter sneaks into.Degassing extruding device of the present invention is the reaction mixture that supply contains polymkeric substance and volatilization composition, and the processing that under reduced pressure outgases is discharged volatile component from outlet, removes the device of the polymkeric substance of volatilization composition from the discharge of polymkeric substance relief outlet.
Therefore, degassing extruding device be provided with the reaction mixture supplying opening that can supply with the reaction mixture that contains polymkeric substance and volatilize composition and
Can discharge from reaction mixture isolate polymkeric substance the polymkeric substance relief outlet and
Can discharge from reaction mixture isolate the volatilization composition one or several outlets and
Revolvable screw rod and
Insert around the insertion mouth of screw rod, be provided with can keep the bubble-tight sealing in inside, the invention is characterized in, it is compared with reaction mixture supplying opening and any position that the outlet position is set, further is provided with gas introduction port in the position of more close axle envelope side.
Shown in Figure 1 is the sketch plan of a configuration example of degassing extruding device of the present invention.The reaction mixture that contains polymkeric substance and volatilization composition, supply with from reaction mixture supplying opening 41, at this moment, because of degassing extruding device inside is decompression state, reaction mixture flashes to vaporific near reaction supplying opening 41, and at least a portion of contained volatilization composition is discharged from exporting 42 in the reaction mixture.Further, reaction mixture advances to right shown in Figure 1 under the effect of screw rod 47 rotations, by encircling 50, pressurization when stopping for the moment, flash distillation once more during by its gap, at least a portion of the volatilization composition in the reaction mixture are gasified again and are discharged from exporting 43.Like this, the major part of volatilization composition is removed from outlet, and can obtain containing the polymkeric substance of a small amount of volatilization composition from polymkeric substance relief outlet 44.In addition, for keeping the decompression state of degassing extruding device inside, around inserting mouth, screw rod sealed with shaft sealing 46.Moreover with reaction mixture supplying opening 41 and export arbitrary position of 42,43 and compare, the position of more close shaft sealing 46 sides is provided with gas introduction port 45, and its structure can make gas import from this gas introduction port 45.
Past, the degassing extruding device of no gas introduction port, when long-term operation, monomer that the volatilization composition is contained and polymkeric substance thereof etc. just near the shaft sealing attached to degassing extruding device, make the polymkeric substance that makes be mixed with foreign matter.Sometimes, shaft sealing is aggregated thing and covers, and makes the running of the screw rod problems such as difficulty that become.Near be considered to the to volatilize monomer composition liquefaction that contained in the composition and being deposited in the axle envelope aggregates into polymkeric substance owing to being heated.This stores disperses, becomes foreign matter, is blended in the polymkeric substance.Degassing extruding device of the present invention, compare with reaction mixture supplying opening and any of position that outlet is set, the position of more close shaft sealing side, be provided with gas introduction port, its formation can import gas from gas introduction port.Degassing extruding device as shown in Figure 1 forms the space at gas introduction port 45 with between exporting 42, and the gas that imports from introducing port forms to right-hand airflow flowing at this.Therefore, volatilization in the composition contained monomer composition etc. just be difficult for arriving near the shaft sealing, even long-term continuous operation, monomer that the volatilization composition is contained and polymkeric substance thereof can not be deposited near the shaft sealing of degassing extruding device yet, thereby can make the polymkeric substance that no foreign matter is sneaked into.
From above situation, gas introduction port preferably is located near the shaft sealing position as far as possible.
Degassing extruding device of the present invention is not particularly limited its set outlet number.Degassing extruding device as shown in Figure 1 is such, and it is also passable to establish two outlets, establishes more than 1 or 3 or 3 also passable.But consider from degassing efficiency and operating cost, preferably establish 2~4 outlets.But when establishing a plurality of outlet, the position is set must be located at than reaction mixture supplying opening and the more close shaft sealing side in all outlet ports position is set of gas introduction port.The position relation of outlet with the reaction mixture supplying opening do not limited yet.But preferably have at least an outlet to be located to compare more close shaft sealing with reaction mixture supplying opening position and survey.The effect that the gas introduction port that looks like degassing extruding device of the present invention is set is just better.
The axle sealing that degassing extruding device of the present invention uses is for known axle envelope composition-formed gets final product.Use mechanical seal, gland seal, Wilson seal, the sealing of O type ring, the ripple sealing all can.Particularly Wilson seal constituted axle sealing is big and preferred to the effect of the set gas introduction port that places degassing extruding device of the present invention.Can use the YG-6080 (trade(brand)name) of silicon company of Toshiba etc. to the used lubricating grease of Wilson seal.
The present invention is not particularly limited employed screw rod radical and structure thereof.From the rerum natura of prepared polymkeric substance, to the product requirements characteristic etc., suitably select to use to get final product.As use screw diameter then can as Φ 30-300mm degree.
As mentioned above, use degassing extruding device of the present invention, even long-term operation does not have polymkeric substance at shaft sealing yet and adheres to and can make the polymkeric substance that no foreign matter is sneaked into.
The invention relates to and have above-mentioned degassing extruding device, polymeric kettle and be connected this polymeric kettle and the manufacturing installation of (methyl) acrylic polymers of the connection section of this degassing extruding device.
Polymeric kettle of the present invention can use the slot type reaction unit that is provided with feedstock composition supplying opening, reaction mixture relief outlet and whipping appts.Whipping appts preferably has the polymeric kettle of making integral body and can both keep mixed performance.In addition, as required, energy heat extraction or the heating mechanism with the polymerization temperature of control setting is set preferably.Temperature is controlled available known method and is carried out.For example establish chuck around the polymeric kettle, carry out temperature control, the thermal medium circulation by the thrust-augmenting nozzle that in polymeric kettle, is provided with or coil pipe etc., carry out temperature control, temperature that also can be by adjusting feedstock composition, carry out temperature control.
Connection section of the present invention can adopt to have the pipe arrangement of carrying reaction mixture liquid, the pump of carrying liquid and the connection section of the well heater that the reacting by heating mixture is used.In addition, also can be provided with mechanical type back pressure valve, relief valve or pressure warning unit formula relief valve equipressure setting device, or the tubular reactor of dress static mixer also can in being provided with.The mechanical type back pressure valve particularly is set makes reaction mixture keep certain pressure, give preferred.The mechanical type back pressure valve is not particularly limited, uses known getting final product.More preferably adopt spring loaded mechanical type back pressure valve.
Shown in Figure 2 is a configuration example of (methyl) of the present invention acrylic polymers manufacturing installation.Have in the polymeric kettle 10 of whipping appts 11, be provided with feedstock composition input port 12 and reaction mixture relief outlet 13.Reaction mixture relief outlet 13, be with the degassing extruding device 40 reaction mixture supplying opening 41 and connection section 20 couple together.Connection section 20 is provided with pump 21 and well heater 22, and it is connected with pipe arrangement 23~25 respectively.
Adopt the manufacturing installation of above-mentioned (methyl) acrylic polymers, because of the volatilization contained monomer of composition and polymkeric substance thereof etc. can screw shaft sealing attached to degassing extruding device near, can make (methyl) acrylic polymers that no foreign matter is sneaked into steadily in the long term continuously.
Shown in Figure 3 is the sectional drawing of an example of the adoptable spring loaded mechanical type of the present invention back pressure valve.This mechanical type back pressure valve has introducing port 71 and relief outlet 72.The liquid that imports from introducing port 71, through voltage stabilizing, can state in pressure-stabilisation under, discharge from relief outlet 72.The structure of this mechanical type back pressure valve, as shown in Figure 3, portion has by valve body 52, spring suppport 53 and valve rod 54 within it, form one, valve 60 moving up and down, between spring suppport 53 and spring capping 55, be provided with spring 56, and at valve 60 bottom, be provided with the valve seat 51 that can contact with valve body 52.When the supply pressure of the liquid of supplying with from supplying opening 71 is low, up can not push away valve 60 and valve body 52 is contact condition with valve seat 51, liquid can not be discharged from relief outlet 72.When the supply pressure of liquid raise, the formed pressure of bounce of supply pressure and spring 56 reached balance and valve 60 is squeezed and shifts top position shown in Figure 3 onto, and liquid just can be from relief outlet 72 outflows.When the supply pressure of liquid changed, valve 60 just moved up and down accordingly, and the liquid of discharging from relief outlet 72 always keeps pressure stable.In addition, by pivoting lid 58, can make and adjust that bolt 57 moves up and down and the force value that can change its setting.The mechanical type back pressure valve can make the liquid pressure of discharge often keep steady state because above-mentioned structure is arranged.When will when above-mentioned connection section uses back pressure valve, being disposed at the position between well heater 22 and the reaction mixture supplying opening 41 by shown in Figure 2.
The mechanical type back pressure valve that the present invention adopts, from being used for making the angle of (methyl) acrylic polymers, its pressure regulation range is preferably between 1~3MPa, more preferably at 1.5~2.5MPa.In addition, " Pa " of the pressure of mechanical type back pressure valve used in the present invention, top hole pressure etc. all is gauge pressure.
Below, describe with regard to the manufacture method of (methyl) of the present invention acrylic polymers.
(methyl) of the present invention acrylic polymers manufacture method is characterized in that having
(A) the feedstock composition that contains (methyl) acrylic monomer, free radical polymerization initiator and chain-transfer agent, supply with continuously polymeric kettle operation and
(B) in polymeric kettle, make above-mentioned (methyl) acrylic monomer, partially polymerized at least and obtain to contain above-mentioned (methyl) acrylic monomer partially polymerized at least (methyl) acrylic polymers the reaction mixture operation and
(C) the operation of this reaction mixture continuous drawing in the above-mentioned polymeric kettle and
(D) the above-mentioned reaction mixture of extracting out from above-mentioned polymeric kettle, import above-mentioned degassing extruding device, the limit imports the processing that outgases of gas, limit from the above-mentioned gas introducing port, and obtains the operation of above-mentioned (methyl) acrylic polymers.
The manufacture method of (methyl) of the present invention acrylic polymers is applicable to the mass polymerization or the solution polymerization of (methyl) acrylic monomer.(methyl) acrylic monomer is not particularly limited, for example, can uses (methyl) alkyl acrylate of the alkyl of carbonatoms 1~18.Concrete have (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) dodecyl acrylate, a stearyl methacrylate etc.These (methyl) acrylic monomers can be used separately, but also two or more is also used.In addition, said here " (methyl) vinylformic acid " is meant methacrylic acid or vinylformic acid (down together).
The present invention is applicable to and contains methyl methacrylate monomer 80 quality % or more than it, further contain the manufacturing of methyl methacrylate units (methyl) alkyl acrylate unitary (methyl) acrylic polymers in addition.At this moment, because (methyl) alkyl acrylate beyond methymethacrylate and the methyl methacrylate, polymerization activity is generally all different, so in the time will making above-mentioned (methyl) acrylic polymers, preferably select the composition of (methyl) acrylic monomer according to its polymerization activity.For example, make that to contain methyl methacrylate units be that 80 quality % and methyl acrylate unit or ethyl propenoate unit are when being (methyl) acrylic polymers of 20% (quality), the composition of (methyl) acrylic monomer, though with the difference of conditions such as the kind of free radical polymerization initiator, polymerization temperature and different, but still the preferable methyl methyl acrylate is about 75 quality %, methyl acrylate or ethyl propenoate are about 25 quality %.
The present invention is not particularly limited the free radical polymerization initiator that adopts.Known free radical polymerization initiators such as organo-peroxide or azo-compounds, separately or two or more be used in combination and get final product.Preferably adopting transformation period under the polymerization temperature of polymeric kettle is 10 seconds~1 hour free radical polymerization initiator.The free-radical initiator that transformation period is too short can make the reaction homogeneity descend, and the free-radical initiator that the transformation period is long easily produces polymer blocks, is difficult to steady running in polymeric kettle.More preferably adopting transformation period under the polymerization temperature of polymeric kettle is 120 seconds~30 minutes free radical polymerization initiator.In addition, the value of " transformation period " of above-mentioned free radical polymerization initiator, for be recorded in Japanese grease (strain) or and light pharmacy known goods catalogues such as (strains) in numerical value.
Have as such free-radical initiator: as tert-butyl hydroperoxide-3,5, the own ester of 5-trimethylammonium, tert-butyl hydroperoxide laurate, tert-butyl hydroperoxide sec.-propyl monocarbonate, uncle's hexyl peroxidation sec.-propyl monocarbonate, tert-butyl hydroperoxide acetic ester, 1, two (tert-butyl hydroperoxide)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (tert-butyl hydroperoxide) hexanaphthenes of 1-, tert-butyl hydroperoxide 2-ethylhexyl, tert-butyl hydroperoxide isobutyl ester, uncle's hexyl peroxidation 2-ethylhexyl, ditertiary butyl peroxide, 2,5-dimethyl-2, organo-peroxides such as two (tert-butyl hydroperoxide) hexanes of 5-; 2--(formamyl azo)-isopropyl cyanide, 1,1 '-azo two (1-cyclohexanenitrile); 2,2 '-Diisopropyl azodicarboxylate, 2; 2 '-azo two (2-methylbutyronitrile), dimethyl 2,2 '-azo isobutyronitrile; 2; 2 '-azo two (2,4, the 4-trimethylpentane); 2,2 '-azo two azo-compounds such as (2-methylpropanes).
The usage quantity of free radical polymerization initiator can be carried out appropriate selection according to the needs of polymerization temperature, productivity, and for example, (methyl) acrylic monomer with respect to 1 mole can use 5.0 * 10
-6~5.0 * 10
-5Amount about mole.
The present invention is not particularly limited chain-transfer agent, as chlorine-containing compound, benzene compound, known chain-transfer agent such as mercaptan compound, separately or two or more be used in combination and all can.But consider preferred mercaptan compound from the angle of the heat-resisting decomposability excellence of (methyl) acrylic polymers of the efficient height of chain-transfer agent, manufacturing.
Have as mercaptan compound: n-butyl mercaptan, isobutyl mercaptan, octyl mercaptan, positive Dodecyl Mercaptan, sec-butyl thioalcohol, secondary Dodecyl Mercaptan, tert.-butyl mercaptan etc. have alkyl or substituted alkyl primary, secondary, uncle's mercaptan compound; Thiophenol, thiocresol, aromatic series thiol compounds such as the 4-tertiary butyl-o-toluene thiophenol; Thiovanic acid and its ester, the mercaptan compound of carbonatomss such as hydroxyethyl mercaptan 3~18 etc.In these mercaptan compounds, tert.-butyl mercaptan, n-butyl mercaptan, octyl mercaptan, particularly suitables such as positive Dodecyl Mercaptan.
About the usage quantity of chain-transfer agent, can need according to rerum natura to select suitable amount to get final product as target (methyl) acrylic polymers.For example, can make the weight average molecular weight (polystyrene standard scaled value) of (methyl) acrylic polymers reach the usage quantity of 70000~150000 scopes for preferred.Specifically, (methyl) acrylic monomer with respect to 100 moles, the usage quantity of chain-transfer agent is 0.01~1.0 mole, preferred 0.05~0.5 mole.Use too much the problem that the polymerization degree that (methyl) acrylic polymers can occur is low, product strength descends.The problem that consumption heat-resisting decomposability very few, that (methyl) acrylic polymers can occur descends.
The present invention, the feedstock composition that contains above-mentioned composition is imported polymeric kettle continuously, in polymeric kettle, make at least a portion polymerization of (methyl) acrylic monomer, obtain contain (methyl) acrylic monomer partially polymerized at least (methyl) acrylic polymers, as reaction mixture.Make the partially polymerized at least this form of (methyl) acrylic monomer, both be applicable to the mass polymerization of not using inert solvent, also be applicable to the solution polymerization of using inert solvent.Particularly preferably be mass polymerization.Even solution polymerization, if the inert solvent amount of using is less than 5 quality % of reaction mixture total amount, just the same with mass polymerization, use small-amount free base initiator just can improve percent polymerization effectively, make good (methyl) acrylic polymers of heat decomposition resistance more efficiently.As in using the solution polymerization system of inert solvent amount more than or equal to 5 quality %, must use a large amount of radical initiating radicals, make the control of polyreaction become difficult.Can use methyl alcohol, ethanol, toluene, dimethylbenzene, acetone, hexone, ethylbenzene, ethyl methyl ketone as inert solvent, the organic solvent that N-BUTYL ACETATE etc. are known.Particularly preferably be methyl alcohol, ethylbenzene, toluene, N-BUTYL ACETATE.Inert solvent can be added in the feedstock composition of (methyl) acrylic monomer of above-mentioned containing, free radical polymerization initiator and chain-transfer agent and use.
Contain in the still poly-, the temperature when making (methyl) acrylic monomer partially polymerized at least can be carried out suitable selecting according to employed raw material type, proportioning etc.Its temperature is controlled available known method and is carried out.As adopt chuck to carry out temperature control, temperature control is carried out in the heating agent circulation of the thrust-augmenting nozzle by being provided with in polymeric kettle, coil pipe etc., also can realize temperature control by the temperature of regulating feedstock composition.
Among the present invention, be provided with containing (methyl) acrylic monomer, at least a portion polymerization the reaction mixture of (methyl) acrylic polymers, the operation of extracting out continuously.Reaction mixture, the mean residence time in polymeric kettle preferably is controlled in 1~6 hour scope.In this scope, controlled polymerization stably, and can make good (methyl) acrylic polymers of molding processability.The residence time is too short, then needs to increase the usage quantity of free-radical initiator, because of the increase of free-radical initiator, makes polyreaction restive, and makes (methyl) acrylic polymers end, and double bond content increases, and is difficult to make the good polymkeric substance of heat-resisting decomposability.Therefore the residence time is more preferably greater than equaling 2 hours.But above-mentioned mean residence time is long, then reduce productivity, and the dipolymer of (methyl) acrylic monomer is increased, more preferably smaller or equal to 5 hours.
In addition, from the reaction mixture that polymeric kettle is derived, the polymkeric substance containing ratio preferably is controlled at 35~65 quality % scopes.The polymkeric substance containing ratio is too high, can produce the problem of the reduction of mixing and heat transfer efficiency, poor stability.The polymkeric substance containing ratio is low excessively, and can make with unreacted (methyl) acrylic monomer is that the volatile matter of main component is difficult to separate.
Usually the reaction mixture heating of extracting out from polymeric kettle, be pressurized to 180~250 ℃, the degree of 1~3MPa, import again and have in the degassing extruding device of above-mentioned gas introducing port, the limit imports the processing that outgases of gas limit from gas introduction port.Gases used nothing is limited especially, air also can, rare gas elementes such as nitrogen, helium, argon also become.If but import air (methyl) acrylic polymers oxidation and degradation may take place.The preferred rare gas element that uses.About importing gas volume, can carry out suitably selectedly then can according to the manufacturing speed etc. of structure, screw diameter and (methyl) acrylic polymers of degassing extruding device, but from making (methyl) acrylic monomer be difficult to arrive shaft sealing, consider that with the separation performance of keeping (methyl) acrylic polymers and volatilization composition the preferred gas flow is 0.5~5 liter/minute.
Among the present invention, preferably has the operation of regulating the pressure of the reaction mixture of extracting out from polymeric kettle with the mechanical type back pressure valve.The mechanical type back pressure valve is not particularly limited.Can use known back pressure valve.But preferably adopt the mechanical type back pressure valve of spring loaded.As mentioned above, reaction mixture one imports the mechanical type back pressure and sends out, and it will be reacted to the supply pressure of the reaction mixture that imports immediately, by moving up and down of valve, makes the reaction mixture of discharging from relief outlet can stably keep desirable pressure.
Among the present invention,, the pressure of the reaction mixture of deriving from polymeric kettle is adjusted to 1~3MPa preferably with the mechanical type back pressure valve.Under hypotensive situation, when the following degassing was handled, making with (methyl) acrylic polymers and unreacted (methyl) acrylic monomer sometimes was the separation of the volatilization composition of the major ingredient difficulty that becomes.Under the situation of hypertonia, the flow velocity of reaction mixture is slack-off, and production efficiency is reduced.More preferably at 1.5~2.5MPa.
The enforcement that the degassing is handled, be under reduced pressure (when for example on being provided with the degassing extruding device of two outlets, handling, the upstream side top hole pressure is adjusted at-0.01~-0.04MPa, the downstream side top hole pressure is adjusted at-0.09~-0.1MPa), be heated to 200~290 ℃, removing with unreacted (methyl) acrylic monomer with regard to separation serially is the major part of the volatilization composition of main composition.In gained (methyl) acrylic polymers, the dipolymer of residual (methyl) acrylic monomer should be controlled at below the 1000 quality ppm, and (methyl) acrylic monomer is preferably smaller or equal to 3000 quality ppm.Like this, can form (methyl) acrylic polymers with high heat-drawn wire and good plastic-molded workability.In addition, residual chain-transfer agent is preferably smaller or equal to 50 quality ppm.Like this, in the time of can suppressing molding processing (methyl) acrylic polymers, because of the problem of heating with last color.Above-mentioned these all can be realized by the pressure of suitably selected degassing processing, the condition of temperature.
When the above-mentioned degassing is handled or thereafter, can be as required, toward (methyl) acrylic polymers in, lubricants such as interpolation higher alcohols, high-grade aliphatic ester class, UV light absorber, thermo-stabilizer, tinting material and antistatic agent etc.
Manufacture method with aforesaid (methyl) acrylic polymers, near the screw shaft sealing of degassing extruding device, do not have monomer and polymkeric substance adheres to, thereby can make (methyl) acrylic polymers that no foreign matter is sneaked into for a long time continuously and stably.
(methyl) acrylic polymers with manufacture method of the present invention and manufacturing installation manufacturing obtain has characteristics such as the good transparency, weathering resistance, can be applicable to various fields such as illumination, billboard class and vehicle.In addition, also be applicable to optical lens, optical applications such as disk basal disc, plastic optical fiber.Moreover, when extrusion molding, also be applicable to long large-scale moulded work and the high thin-walled moldings of setting resin temperature of the residence time in tube.
Description of drawings
Fig. 1 is the sketch chart of an in-built embodiment of expression degassing extruding device of the present invention.
Fig. 2 is the pie graph of an embodiment of manufacturing installation of expression (methyl) of the present invention acrylic polymers.
Fig. 3 is the sectional view of an example of the used mechanical type back pressure valve of the present invention.
Nomenclature
10 polymeric kettles
11 whipping apptss
12 feedstock composition input ports
13 reaction mixture relief outlets
20 connection sections
21 pumps
22 well heaters
23~25 pipe arrangements
40 degassing extruding devices
41 reaction mixture relief outlets
42,43 outlets
44 polymkeric substance relief outlets
45 gas introduction ports
46 shaft sealings
47 screw rods
50 rings
51 valve seats
52 valve bodies
53 spring suppports
54 valve rods
55 spring cappings
56 springs
57 adjust bolt
58 lids
60 valves
71 introducing ports
72 relief outlets
Embodiment
[embodiment]
Below, describe the present invention in detail with embodiment.
(embodiment 1)
The feedstock composition 1 by following proportioning, supply is provided with in the slot type reaction unit of whipping appts, carries out polyreaction under 135 ℃ of polymerization temperatures of setting, 3 hours condition of mean residence time.
(feedstock composition 1)
Methyl methacrylate (MMA) 98.0 mass parts
Methyl acrylate (MA) 2.0 mass parts
Octyl mercaptan 0.25 mass parts
Tert-butyl hydroperoxide 3,5, the own ester of 5, one trimethylammoniums (MMA and MA are added up to total amount)
70 quality ppm
The reaction mixture of extracting out from the slot type reaction unit, after using the well heater formed by multi tube heat exchanger, being heated to 220 ℃, by means of manual pressure regulating valve, import in the single shaft degassing extruding device (150mm, screw rod L/D28) of structure as shown in Figure 1, outgasing, (260 ℃, the pressure of outlet pressure-0.02MPa of 42, outlet 43-0.097MPa) were made (methyl) acrylic polymers in continuous 5 days in processing.In addition, from the gas introduction port of degassing extruding device, import flow and be 1.5 liters/minute nitrogen, the limit imports the gas limit and implements the degassing and handle, even make after the beginning through 5 days, also not finding has stores at the screw shaft sealing.On-stream, the pressure stability of the reaction mixture of supply degassing extruding device is poor slightly, needs the fine setting relief valve.Moreover, the pressure of the reaction mixture of importing degassing extruding device, target value is 2.1MPa.
With (methyl) acrylic polymers section that obtains, under 260 ℃ of tube temperature, carry out the plate of injection-molded making 100mm * 100mm * 2mm, through confirming that the plate that makes does not have foreign matter, appearance transparent.
(embodiment 2)
Except that changing to the air from the gas introduction port of degassing extruding device, the gas of importing, other with embodiment 1 identical operations, makes (methyl) acrylic polymers.Even through 5 days, portion did not find stores yet in the screw shaft envelope after the manufacturing beginning.
With (methyl) acrylic polymers section that obtains, carry out molding 260 ℃ of tube temperature and make 100mm * 100mm * 2mm plate, through confirming that the plate that makes does not have foreign matter, outward appearance is slightly yellow, transparent.(embodiment 3)
Except that well heater and the degassing extruding device between, establish the mechanical type back pressure valve operation manufacturing (methyl) acrylic polymers similarly to Example 1.The mechanical type back pressure valve, use be (strain) bank river particular usage valve system R-F-93703-3-1 (trade(brand)name, high pressure with 40 * 40 back pressure valves).The initial setting pressure of back pressure valve is 2.1MPa.
Turned round in continuous 5 days, the pressure of supplying with the reaction mixture of degassing extruding device can often keep certain (2.1MPa), does not find also that through 5 days the screw shaft sealing has stores after the manufacturing beginning.
With the section of making (methyl) acrylic polymers that beginning obtains after 5 days, under 260 ℃ of tube temperature, carry out injection-molded, making 100mm * 100mm * 2mm plate.Through confirming that the plate that makes does not have foreign matter, appearance transparent.
(reference examples 1)
Except that the gas introduction port from degassing extruding device does not import the no gas, with embodiment 2 identical operations manufacturing (methyl) acrylic polymerss.Making the beginning back in the time of the 24th hour, confirming that the screw shaft sealing has dirt settling.
With making (methyl) acrylic polymers section that beginning made after 5 days, 260 ℃ of tube temperature, carry out injection-molded, making 100mm * 100mm * 2mm plate.Confirm that the plate that makes has foreign matter to exist.
Claims (9)
1. degassing extruding device, it has
Can supply with the reaction mixture contain polymkeric substance and volatilization composition the reaction mixture supplying opening and
Can discharge the described polymkeric substance from this reaction mixture, separate the polymkeric substance relief outlet and
Can discharge the described volatilization composition from this reaction mixture, separate one or more outlets and
Revolvable screw rod and
Be arranged at and can keep inner bubble-tight shaft sealing around the insertion mouth that inserts this screw rod,
It is characterized in that, than described reaction mixture supplying opening and described outlet position is set any one compare, further be provided with gas introduction port in the position of more close described shaft sealing side.
2. degassing extruding device as claimed in claim 1, at least one in its described outlet is arranged on than being located at described reaction mixture supplying opening position and compares the position of more close described shaft sealing side.
3. degassing extruding device as claimed in claim 1, its described shaft sealing is made up of Wilson seal.
4. the manufacturing installation of (methyl) acrylic polymers, the connection section that it has the described degassing extruding device of claim 1, polymeric kettle and is connected this polymeric kettle and degassing extruding device.
5. the manufacturing installation of (methyl) as claimed in claim 4 acrylic polymers, it is provided with the mechanical type back pressure valve at described connection section.
6. the manufacture method of (methyl) acrylic polymers is characterized in that having
(A) the feedstock composition that contains (methyl) acrylic monomer, free radical polymerization initiator and chain-transfer agent supply with continuously polymeric kettle operation and
(B) in this polymeric kettle, make described (methyl) acrylic monomer partially polymerized at least and obtain to contain described (methyl) acrylic monomer partially polymerized at least (methyl) acrylic polymers reaction mixture operation and
(C) the operation of this reaction mixture continuous drawing in the described polymeric kettle and
(D) the described reaction mixture that extracts from described polymeric kettle is imported the described degassing extruding device of claim 1, and from described gas introduction port, the limit imports gas, limit and outgases and handle and obtain the operation of described (methyl) acrylic polymers.
7. the manufacture method of (methyl) as claimed in claim 6 acrylic polymers, it is a rare gas element from the gas that described gas introduction port imports.
8. the manufacture method of (methyl) as claimed in claim 6 acrylic polymers, it is 0.5~5 liter/minute from the gas flow that described gas introduction port imports
9. the manufacture method of (methyl) as claimed in claim 6 acrylic polymers, it also has by the mechanical type back pressure valve, adjusts from the operation of the pressure of the continuous described reaction mixture of deriving of described polymeric kettle.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2003344562A JP4216682B2 (en) | 2003-10-02 | 2003-10-02 | (Meth) acrylic polymer production apparatus and (meth) acrylic polymer production method |
JP2003344562 | 2003-10-02 | ||
JP2003348300A JP4459587B2 (en) | 2003-10-07 | 2003-10-07 | Method for producing (meth) acrylic polymer using devolatilization extrusion equipment |
JP2003348300 | 2003-10-07 |
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CN1618820A true CN1618820A (en) | 2005-05-25 |
CN100417667C CN100417667C (en) | 2008-09-10 |
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CN104411733A (en) * | 2012-06-29 | 2015-03-11 | 株式会社可乐丽 | Method for producing (meth)acrylic resin composition |
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JP5140117B2 (en) * | 2010-07-08 | 2013-02-06 | 住友化学株式会社 | A devolatilizing extruder for a (meth) acrylic polymer, a devolatilizing extrusion method for a polymer composition using the same, and a method for producing a (meth) acrylic polymer |
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JP4753062B2 (en) * | 2001-05-08 | 2011-08-17 | 独立行政法人 日本原子力研究開発機構 | Method and apparatus for radiation graft polymerization of fiber material |
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CN104411733A (en) * | 2012-06-29 | 2015-03-11 | 株式会社可乐丽 | Method for producing (meth)acrylic resin composition |
CN104411733B (en) * | 2012-06-29 | 2016-08-24 | 株式会社可乐丽 | The manufacture method of (methyl) acrylic resin composition |
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