CN100448639C - 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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- CN100448639C CN100448639C CNB2004100811489A CN200410081148A CN100448639C CN 100448639 C CN100448639 C CN 100448639C CN B2004100811489 A CNB2004100811489 A CN B2004100811489A CN 200410081148 A CN200410081148 A CN 200410081148A CN 100448639 C CN100448639 C CN 100448639C
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Abstract
Provided is a devolatilizing extrusion apparatus capable of incorporating an additive in an accurate amount into a polymer without causing contamination of volatile components with the additive, and a manufacturing apparatus and a manufacturing method capable of manufacturing a (meth)acrylic polymer containing the additive in an accurate amount. The devolatilizing extrusion apparatus is provided with a reaction mixture-feeding port capable of feeding a reaction mixture containing the polymer and the volatile components, a polymer-discharging port capable of discharging the polymer separated from the reaction mixture, one or more vents capable of discharging the volatile components separated from the reaction mixture, a rotatable screw, and an additive-feeding port installed at a position nearer to the polymer-discharging port than the position of the vent installed at the nearest position from the polymer-discharging port, and further provided with a mechanism for causing the polymer to temporarily stay between the position of the vent installed at the nearest position from the additive-feeding port and the position where the additive-feeding port is installed.
Description
Technical field
The present invention relates to a kind of employed degassing extruding device during by continuous polymerization manufactured (methyl) acrylic polymer, use the manufacturing installation and the manufacture method of (methyl) acrylic polymer of this device.
Background technology
(methyl) acrylic polymer of the prepared polymethyl methacrylate of polymerization methyl methacrylate etc. (methyl) acrylic monomer (PMMA) etc. has characteristics such as the transparency, gasproof marquis property, good appearance, can be applicable to various fields such as illumination, billboard class and vehicle.Also be widely used in optical applications such as optical lens, disk basal disc, plastic optical fiber.
As the manufacture method of (methyl) acrylic polymer, the general suspension polymerizations that adopt more.But because used auxiliary agents such as suspension dispersive agent, sneak in (methyl) acrylic polymer, make its transparency poor and be not suitable for optical applications.In addition, because miscellaneous operations such as manufacture process needs to filter, washs, drying, and productivity ratio is reduced.
As the manufacture method of (methyl) acrylic polymer, except that above-mentioned suspension polymerization, also have methods such as known polymerisation in bulk, polymerisation in solution.Use these methods, can make (methyl) acrylic polymer that the transparency does not reduce, has good characteristic.Recently, noticeable is the solution polymerization process that adopts mass polymerization or contain a small amount of solvent, the continuous polymerization that can make continuously, boost productivity.But when adopting these methods to make (methyl) acrylic polymer,, will produce " gel effect ", and cause the phenomenon that polymerization rate sharply increases in case the containing ratio of this polymer uprises.Promptly under the higher state of polymer containing ratio, be difficult to the stable polymerisation of control.
Therefore, for realizing stable polymerisation, be everlasting the low stage of polymer containing ratio, finish polymerisation, obtain contain (methyl) acrylic polymer and with unreacted (methyl) acrylic monomer be Main Ingredients and Appearance, the volatilization composition reactant mixture, extract out from polymeric kettle, heat, pressurize, importing has in the degassing extruding device of outlet.In the degassing extruding device of inner pressure relief state, the volatilization composition of removing in the reactant mixture to be contained, and obtain (methyl) acrylic polymer as target.For example, the spy opens clear 50-40688 communique, and the reactant mixture that obtains is pressurized to more than or equal to 20kg/cm
2, be heated to 210～270 ℃, import and to adjust to more than or equal to 50torr, smaller or equal to the feed portion of atmospheric degassing extruding device, at this moment, the pressure and temperature of outlet is adjusted to respectively smaller or equal to 50torr, 250～290 ℃, made the manufacture method of volatilization composition poor (methyl) acrylic polymer.
In addition, when containing (methyl) acrylic polymer of additives such as lubricant (releasing agent), ultra-violet absorber, heat stabilizer, colouring agent and antistatic additive such as higher alcohols, high-grade aliphatic ester class when manufacturing, from being arranged on the additive input port of degassing extruding device, drop into additive.But this moment, the part of input additive can together be discharged from outlet with the volatilization composition, therefore is difficult to make (methyl) acrylic polymer of the additive that contains accurate amount.Moreover, also has the problem of from the volatilization composition that outlet is discharged, sneaking into additive.As sneak into additive in the composition that volatilizees, according to circumstances additive might become the reason that outlet, pipe arrangement etc. stop up, simultaneously, as want to be provided with the treatment process of separate addn sometimes in addition under the situation of (methyl) acrylic monomer in the recycling volatilization composition.
Summary of the invention
In view of above situation, purpose of the present invention, provide the additive of accurate amount is mixed in the polymer, and additive can not sneaked into the manufacturing installation and the manufacture method of (methyl) acrylic polymer that evaporates in one's duty degassing extruding device and can make the additive that contains accurate amount.
Degassing pressure device of the present invention, it has
Can supply with the reactant mixture contain polymer and volatilization composition the reactant mixture supply port and
Can discharge the above-mentioned polymer of separating from this reactant mixture the polymer outlet and
One or more outlets of the above-mentioned volatilization composition that discharge can be separated from this reactant mixture and
Rotatable screw rod and
Than being arranged at the position of the above-mentioned outlet of the most close above-mentioned polymer outlet position, be provided with the additive input port in the position that more close above-mentioned polymer is discharged oral-lateral,
It is characterized in that, be arranged on the above-mentioned exit position of position, the most close above-mentioned additive input port and be provided with between the position, above-mentioned additive input port, further have and make the temporary transient structure that stops of above-mentioned polymer.Such a degassing extruding device can make the additive of accurate amount be mixed in the polymer, does not go and additive is blended in the volatilization composition.
Above-mentioned degassing extruding device, the structure that above-mentioned polymer is stopped for the moment that is had preferably are arranged on the ring of above-mentioned screw rod or are arranged on the threaded shank of the reverse propulsion of above-mentioned screw rod.
Embodiment preferred for this invention is to be provided with above-mentioned degassing extruding device, polymeric kettle and to be connected this polymeric kettle and the manufacturing installation of (methyl) acrylic polymer of the connecting portion of this degassing extruding device.
Embodiment preferred for this invention, be adopt above-mentioned degassing extruding device and have
(A) the feedstock composition that contains (methyl) acrylic monomer, free radical polymerization initiator and chain-transferring agent supply with continuously polymeric kettle operation,
(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 (methyl) acrylic polymer the reactant mixture operation,
(C) operation that this reactant mixture is extracted out continuously from above-mentioned polymeric kettle,
(D) the reactant mixture of extracting out from above-mentioned polymeric kettle, import above-mentioned degassing extruding device outgas the operation handled,
(E) drop into the manufacture method of (methyl) acrylic polymer of the operation of additive from above-mentioned additive input port.
As adopt degassing extruding device of the present invention, and in polymer, can mix the additive of accurate amount, additive can be blended in the volatilization composition go.In addition, can become the manufacturing installation and the manufacture method of (methyl) acrylic polymer of making the additive that contains accurate amount.Therefore, additive can not become the reason of outlet, pipe arrangement obstruction.In addition, as reclaiming, when utilizing (methyl) acrylic monomer in the volatilization composition again, also need not to establish in addition the processing of separate addn.
Degassing extruding device of the present invention, it is the reactant mixture that contains polymer and volatilization composition in order to supply with, processing under reduced pressure outgases, on the one hand the volatilization composition of separating is discharged from outlet, on the other hand, additive package in the polymer of removing the volatilization composition, and the polymer that contains additive discharged from the polymer outlet.Therefore, this degassing extruding device be provided with can supply with contain polymer and the volatilization composition reactant mixture the reactant mixture supply port and
Can discharge the polymer of separating from reactant mixture the polymer outlet and
Can discharge the volatilization composition of separating from reactant mixture one or more outlets and
Revolvable screw rod and
Compare with the exit position that the most close polymer outlet position is set, the position of discharging oral-lateral at more close polymer is provided with the additive input port,
It is characterized in that between set exit position, the position of the most close additive input port and position, additive input port, further having the structure that polymer is stopped for the moment.
Fig. 1 represents the outgas skeleton diagram of extruding device one configuration example of the present invention.The reactant mixture that contains polymer and volatilization composition is supplied with from reactant mixture supply port 41.At this moment, because of degassing extruding device inside is decompression state, reactant mixture flashes to vaporific near reactant mixture supply port 41, and at least a portion of the volatilization composition that reactant mixture is contained is discharged from exporting 42.And then because the turning effort of screw rod 47, reactant mixture is advanced to right as shown in Figure 1, because ring 51 pressurization when stopping for the moment, when by its gap, flash distillation once again, at least a portion of the volatilization composition that reactant mixture is contained gasifies and discharges from exporting 43.Like this, the major part of volatilization composition is discharged from outlet, forms the polymer that contains a small amount of volatilization composition.At this moment, drop into additive from the additive input port that the position was provided with of comparing more close polymer outlet 44 sides with set outlet 43 positions, the most close polymer outlet 44 positions, with mixed with polymers, the polymer that contains additive is discharged from polymer outlet 44.In addition, be to keep the decompression state of degassing extruding device inside, inserted screw rod 47 the insertion mouth around seal by shaft sealing 46.
Moreover, stop for the moment between the position of the position of the set outlet 43 in the position of the most close additive input port 49 and the additive input port 49 that is provided with for making polymer, be provided with ring 48 in the relevant position of screw rod 47.This ring 48 is different with the effect of above-mentioned ring 51, and it is not for flash distillation, and polymer is stopped for the moment, with resting on the ring that the polymer of additive input port 49 with outlet 43 opened its blocking.Therefore, be necessary closely to be full of the polymer that makes about gas can not move for 48 pairs at ring.
Past, insert the degassing extruding device of the screw rod that does not have ring, when when a part of additive is dropped in the additive input port, itself and volatilization composition are discharged from outlet together, this not only makes the additive of accurate amount be mixed into and becomes difficult in (methyl) acrylic polymer, also cause the problem of having sneaked into additive from the volatilization composition that outlet is discharged.As sneak into additive in the composition that volatilizees, according to circumstances additive might become the reason that outlet, pipe arrangement etc. stop up.In addition, as when wanting (methyl) acrylic monomer in the recycling volatilization composition, the treatment process that may also will establish separate addn in addition.Degassing extruding device of the present invention, between the set position in the position of the outlet that is provided with in position, the most close additive input port and additive input port, owing to have the structure that polymer is stopped for the moment, can open additive input port and outlet blocking by the polymer that stops for the moment.That is, the additive that drops into from the additive input port is just difficult discharges from outlet, makes the additive that mixes accurate amount in the polymer become possibility.Degassing extruding device for example shown in Figure 1, because the effect of the ring 48 of screw rod 47, polymer is paid in the left side of ring 48 and is stopped nearly a period of time, interdict additive input port 49 with between exporting 43 with this polymer and come, thereby 49 additives that drop into just can not discharged from outlet from the additive input port.
The present invention does not have special restriction to the structure that polymer is stopped for the moment, as long as polymer is stopped for the moment, has with this polymer the function opened of blocking between additive input port and the outlet just not necessarily is only limited to the above-mentioned ring that is provided with on screw rod.It is the threaded shank that is provided with reverse propulsion on screw rod that other preferred implementation can be enumerated the structure that the polymer of sening as an envoy to stops for the moment.Shown in Figure 2 is a configuration example of having inserted the degassing extruding device of the threaded shank with reverse propulsion.Such a degassing extruding device, the same with degassing pressure device shown in Figure 1, rely on the reverse propulsion threaded shank 50 of screw rod 47, polymer is stopped for the moment in additive input port 49 with between exporting 43, interdicted additive input port 49 with between exporting 43 by this polymer and to open (polymer is full of therebetween), then the additive that drops into from the additive input port just can not discharged from outlet.In addition, in the tube inboard of the degassing extruding device institute allocation projection being set, so that polymer stops for the moment in additive input port 49 with between exporting 43, also is embodiment preferably.
Screw rod number and structure thereof except that have above-mentioned making the structure that polymer stops for the moment according to needs, do not have restriction especially.Get final product from require considerations such as characteristic suitably to select for use to the rerum natura of polymer and to goods.But under the situation of the screw rod that has ring, can list the preferably formation of single screw rod,, can select the screw rod about Φ 50～300mm for use as screw diameter.
Degassing extruding device of the present invention does not have special restriction to set outlet number, as the degassing extruding device of Figure 1 and Figure 2, establish two outlets also can, establish more than 1 or 3 or 3 and also can.But consider that from degassing efficiency and operating cost the degassing extruding device of establishing 2～4 outlets is more suitable to the present invention.But when establishing a plurality of outlet, the additive input port must be located to be compared more close polymer with all outlet ports position and discharges oral-lateral.
In addition, degassing extruding device of the present invention is compared with reactant mixture supply port and any one position of exporting set position, and it is better to be provided with gas introduction port again in the position of more close shaft sealing side.Import inert gas from this gas introduction port like this, just can not pay at shaft sealing does not closely have monomer or its polymer buildup, can prevent from that foreign matter is blended in the goods to go.
Degassing extruding device of the present invention, the shaft sealing that is adopted are as long as form known axle envelope mode, and as mechanical seal, the gland envelope is close, Wilson seal, and the sealing of O type ring, ripple sealing etc. all can be used.Particularly form the degassing extruding device of shaft sealing, because it is bigger and suitable that the effect of picture above-mentioned gas introducing port is set by Wilson seal.As the lubricating grease that uses in Wilson seal, as using the made YG-6080 (trade name) of silicon society of Toshiba etc.
As mentioned above, use degassing extruding device of the present invention, but the additive of precise control amount be mixed in the polymer, can avoid additive be blended into the volatilization composition in.Therefore, the reason that additive can not cause outlet, pipe arrangement etc. to stop up is reclaiming, when utilizing (methyl) acrylic monomer in the volatilization composition again, also need not to establish in addition the treatment process of separate addn.
Moreover, the invention relates to and be provided with above-mentioned degassing extruding device, polymeric kettle and be connected this polymeric kettle and the manufacturing installation of (methyl) acrylic polymer of the connecting portion of this degassing extruding device.
Polymeric kettle of the present invention can use the slot type reaction unit that is provided with feedstock composition supply port, reactant mixture outlet and agitating device is housed.Agitating device preferably has makes polymeric kettle integral body can both keep the performance of mixing.In addition, as required, preferably be provided with energy heat extraction or heating structure with the polymerization temperature of control setting.The temperature control structure can be carried out with known structure.For example the structure of establishing chuck around polymeric kettle by the structure to circulating thermal mediums such as mozzle that is provided with or coil pipes, also can be carried out temperature controlled structure by the temperature of adjusting feedstock composition in polymeric kettle.
Connecting portion of the present invention can use to have for the pipe arrangement of carrying reactant mixture, carry the pump that liquid uses and the heater of reactant mixture heating usefulness.In addition, also can be provided with the pressure-regulating device of mechanical type counterbalance valve, pressure regulator valve or pressure gauge formula pressure regulator valve etc., or the tubular reactor of dress static mixer also can in being provided with.Particularly one the mechanical type counterbalance valve is set, just can makes reactant mixture keep certain pressure, so preferred.
Shown in Figure 3 is a configuration example of the present invention's (methyl) acrylic polymer manufacturing installation.The polymeric kettle 10 of agitating device 11 is housed, is provided with feedstock composition input port 12 and reactant mixture outlet 13.As shown in Figure 1, reactant mixture outlet 13, be by the degassing extruding device 40 reactant mixture supply port 41 and connecting portion 20 couple together.Be provided with pump 21 and heater 22 at connecting portion, it is connected with pipe arrangement 23～25 respectively.
Use above-mentioned (methyl) acrylic compounds manufacturing installation, the additive that drops into from the additive input port can not discharged from outlet, can make (methyl) acrylic polymer of the additive that contains accurate amount.Therefore, additive also can not become the plugging reason of outlet, pipe arrangement etc.As during (methyl) acrylic monomer of wanting to be contained in the recycling volatilization composition, the processing that also needn't establish separate addn in addition.
Below describe with regard to the manufacture method of (methyl) of the present invention acrylic polymer.
The manufacture method of (methyl) of the present invention acrylic polymer, it is characterized in that it has
(A) the feedstock composition that contains (methyl) acrylic monomer, free radical polymerization initiator and chain-transferring agent supply with continuously polymeric kettle operation and
(B) in this polymeric kettle, make at least a portion polymerization of above-mentioned (methyl) acrylic monomer and obtain to contain above-mentioned (methyl) acrylic monomer to the operation of the reactant mixture of (methyl) acrylic polymer of small part polymerization and
(C) this reactant mixture from the operation of above-mentioned polymeric kettle continuous drawing and
(D) the above-mentioned reactant mixture that extracts from above-mentioned polymeric kettle, import above-mentioned degassing extruding device outgas the operation handled and
(E) drop into the operation of additive from above-mentioned additive input port.
The manufacture method of (methyl) of the present invention acrylic polymer is highly suitable for the polymerisation in bulk or the polymerisation in solution of (methyl) acrylic monomer.(methyl) acrylic monomer is not particularly limited, as (methyl) alkyl acrylate with alkyl of carbon number 1～18 all can use.Concrete have (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) dodecyl acrylate, (methyl) octadecyl acrylate etc.These (methyl) acrylic monomers can be used separately, but also two or more is also used.In addition, said here " methacrylic acid " is meant methacrylic acid or acrylic acid (down together).
The present invention is applicable to and makes the methyl methacrylate units that contains more than or equal to 80 quality %, further contains (methyl) acrylic polymer of methyl methacrylate units (methyl) acrylic acid alkyl ester units in addition.At this moment, because methyl methacrylate is generally all different with the polymerization activity of methyl methacrylate (methyl) alkyl acrylate in addition, so in the time will making above-mentioned (methyl) acrylic polymer, suitably select the composition of (methyl) acrylic monomer according to its polymerization activity.For example, as will make (methyl) acrylic polymer that contains 80 quality % methyl methacrylate units and 20 quality % methyl acrylate unit or ethyl acrylate unit the time, (methyl) though the composition of acrylic monomer with the difference of conditions such as the kind of free radical polymerization initiator, polymerization temperature and different, but still the methyl methacrylate about preferred 75 quality %, methyl acrylate or the ethyl acrylate about 25 quality %.
The free radical polymerization initiator that uses among the present invention is not particularly limited.Known free radical polymerization initiators such as known organic peroxide or azo-compound, can be separately or two or more be used in combination.Preferably use under the polymerization temperature of polymeric kettle, the half-life is 10 seconds～1 hour a free radical polymerization initiator.The free-radical initiator that half-life is too short can make the reaction homogeneity descend, and the free-radical initiator that the half-life is long easily produces polymer blocks, is difficult to steady running in polymeric kettle.It is preferred that to be to use half-life under the polymerization temperature of polymeric kettle be 120 seconds～30 minutes free radical polymerization initiator.In addition, the value of " half-life " of above-mentioned free radical polymerization initiator, for Japanese grease (strain) or and light pharmacy known goods catalogues such as (strains) in the numerical value put down in writing.
As such free-radical initiator, can enumerate, for example tert-butyl hydroperoxide 3,5, the own ester of 5-trimethyl, tert-butyl hydroperoxide laurate, tert-butyl hydroperoxide isopropyl monocarbonate, uncle's hexyl peroxidating isopropyl monocarbonate, tert-butyl hydroperoxide acetate, 1, two (tert-butyl hydroperoxides) 3 of 1-, 3,5_ trimethyl-cyclohexane, 1, two (tert-butyl hydroperoxide) cyclohexanes of 1_, tert-butyl hydroperoxide 2_ Octyl Nitrite, tert-butyl hydroperoxide isobutyl ester, uncle's hexyl peroxidating 2_ Octyl Nitrite, di-tert-butyl peroxide, 2,5_ dimethyl-2, organic peroxides such as two (tert-butyl hydroperoxide) hexanes of 5-; 2__ (carbamoyl azo) _ isobutyronitrile, 1,1 ' _ azo two (1_ cyclohexanenitrile); 2,2 ' _ azodiisobutyronitrile, 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 use amount of free radical polymerization initiator can be carried out suitable selection according to the needs of polymerization temperature, productivity ratio, 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-transferring agent, as chlorine-containing compound, benzene compound, known chain-transferring agent such as mercaptan compound, separately or two or more be used in combination and all can.But consider preferred mercaptan compound from the good angle of heat-resisting decomposition of (methyl) acrylic polymer of the high efficiency of chain-transferring agent, manufacturing.
Have as mercaptan compound: n-butyl mercaptan, isobutyl mercaptan, n-octyl mercaptan, positive lauryl mercaptan, sec-butyl thioalcohol, secondary lauryl mercaptan, tert-butyl mercaptan etc. have alkyl or substituted alkyl primary, secondary, uncle's mercaptan compound; Benzenethiol, thiocresol, the 4-tert-butyl group _ neighbour _ aromatic mercaptans compounds such as thiocresol; TGA and its ester, the mercaptan compound of carbon numbers such as ethoxy mercaptan 3～18 etc.In these mercaptan compounds, more preferably tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, positive lauryl mercaptan etc.
About the use amount of chain-transferring agent, be considered as target (methyl) acrylic polymer rerum natura and select suitable amount to get final product.For example, preferably can make (methyl) acrylic polymer weight average molecular weight (polystyrene standard scaled value), reach the use amount of 70000～150000 scopes.Concrete, (methyl) acrylic monomer with respect to 100 moles, the use amount of chain-transferring agent is 0.01～1.0 mole, preferred 0.05～0.5 mole.Use too much the problem that the degree of polymerization that (methyl) acrylic polymer can occur is low, product strength descends.Consumption is very few, the problem of the heat-resisting decomposability decline of (methyl) acrylic polymer can occur.
The present invention is the feedstock composition that contains above-mentioned composition, import polymeric kettle continuously, in polymeric kettle, make at least a portion polymerization of (methyl) acrylic monomer, obtain contain (methyl) acrylic monomer to small part polymerization, (methyl) acrylic polymer, as reactant mixture.Make the partially polymerized at least this form of (methyl) acrylic monomer, both be applicable to the polymerisation in bulk of not using atent solvent, also be applicable to the polymerisation in solution of using atent solvent.More preferably be used for polymerisation in bulk.Even polymerisation in solution, if the atent solvent amount of using is less than 5 quality % of reactant mixture total amount, also the same with polymerisation in bulk, use small-amount free base initator just can improve aggregate rate effectively, can make good (methyl) acrylic polymer of heat decomposition resistance efficiently, so preferred.As in using the solution polymerization system of atent solvent amount more than or equal to 5 quality %, be necessary to use a large amount of free-radical initiators, polymerisation is difficult to control.As atent solvent, can use methyl alcohol, ethanol, toluene, dimethylbenzene, acetone, methyl iso-butyl ketone (MIBK), ethylbenzene, methyl ethyl ketone, known organic solvent such as butyl acetate.More preferably methyl alcohol, ethylbenzene, toluene, butyl acetate.Atent solvent can be added in the feedstock composition that contains above-mentioned (methyl) acrylic monomer, free radical polymerization initiator and chain-transferring agent and use.
Contain in the still poly-, the temperature when making at least a portion polymerization of (methyl) acrylic monomer can be carried out suitable selected according to employed raw material type, match ratio etc.Its temperature is controlled available known method.For example, can adopt the temperature control that chuck carries out, the temperature control of being undertaken by the thermal medium circulation of the mozzle that in polymeric kettle, is provided with or coil pipe etc., the method for carrying out temperature control etc. by the temperature of adjusting feedstock composition.
Among the present invention, be provided with contain (methyl) acrylic monomer at least a portion the reactant mixture of (methyl) acrylic polymer of polymerization from the poly-operation of extracting out continuously the still that contains.The mean residence time of reactant mixture in polymeric kettle is preferably in 1～6 hour scope.In this scope, can stably control polymerization, simultaneously, can produce good (methyl) acrylic polymer of molding processability.The time of staying is too short, just need to increase the use amount of free-radical initiator, because the increase of free-radical initiator makes polymerisation restive, (methyl) acrylic polymer terminal double bond content is increased, and can not get the good polymer of heat-resisting decomposability.Therefore the time of staying is more preferably greater than equaling 2 hours.On the other hand, above-mentioned mean residence time is long, when reducing productivity ratio, the dimer of (methyl) acrylic monomer is increased, so not preferred.Be more preferably less than and equal 5 hours.
In addition, from the reactant mixture that polymeric kettle is derived, the scope of preferred 35～65 quality % of polymer containing ratio.The polymer containing ratio is too high, will produce the problem of the reduction of mixing and heat transfer efficiency, bad stability.The polymer 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 reactant mixture of extracting out from polymeric kettle, heat, be pressurized to about 180～250 ℃, 1～3MPa (gauge pressure) after, import and be provided with in the degassing extruding device of above-mentioned additive input port, processing outgases.The degassing is handled, it is the reactant mixture that imports continuously, decompression [for example the upstream side outlet pressure adjust to-0.01～-0.04MPa (gauge pressure) about, the downstream side outlet pressure adjusts to-0.09～-0.1MPa (gauge pressure) about] under, be heated to 200～290 ℃, separate continuously that to remove with unreacted (methyl) acrylic monomer be the major part volatilization composition of Main Ingredients and Appearance.In (methyl) acrylic polymer that finally obtains, the dimer of remaining (methyl) acrylic monomer is preferably smaller or equal to 1000ppm, and (methyl) acrylic monomer is preferably smaller or equal to 3000ppm.Thus, can form (methyl) acrylic polymer with higher heat distortion temperature, good plastic-molded workability.In addition, remaining chain-transferring agent is preferably smaller or equal to 50ppm.Like this, can suppress (methyl) acrylic polymer when processing and forming because the heating and painted problem.These can be realized by the pressure of suitably selected degassing processing, the condition of temperature.In addition, " ppm " here is quality ppm.
In addition, drop into additive from the additive input port that is located at degassing extruding device.Can use lubricant (releasing agent), ultra-violet absorber, heat stabilizer, colouring agent and the antistatic additive of higher alcohols, high-grade aliphatic ester class etc. as additive.Market sale product as releasing agent have: reason is ground the system リ ケ マ one Le S-100A (trade name) of vitamin society, and Hua Wangshe system カ Le コ one Le 8688 (trade name) Japan becomes wax society system paraffin 115 (trade name) etc.There is ッ Block ロ to change into system ッ one ソ of society one Block 701 (trade name), Xu Dianhuagongyeshe system ァ デ カ ス Block LA-36 (trade name) etc. as ultra-violet absorber.At this, adopt degassing extruding device of the present invention, the additive of input can not discharged from outlet, so the ormal weight that the input amount of additive is equivalent to be contained in as (methyl) acrylic polymer of object gets final product.Like this, the additive of input can not discharged from outlet, and mixes with (methyl) acrylic polymer, can make (methyl) acrylic polymer that contains additive.
Adopt the manufacture method of above-mentioned (methyl) acrylic polymer, because additive can be from the outlet discharge, so can make (methyl) acrylic polymer that contains accurate amount additive.Therefore, additive can not become the reason that outlet, pipe arrangement etc. stop up yet.In addition, as want the occasion of (methyl) acrylic monomer contained in the recycling volatilization composition, separation, the processing that also needn't establish additive in addition.
Adopt manufacture method of the present invention and manufacturing installation, prepared (methyl) acrylic polymer is applied flexibly its good transparency, against weather etc., can be applicable to various fields such as illumination, billboard class, vehicle.Also be applicable to optical applications such as optical lens, disk basal disc, plastic optical fiber.In addition, when injection moulding, also be applicable to long large part and the high thin-walled mechanograph of setting resin temperature of the time of staying in tube.
Description of drawings
Fig. 1 is the internal structure skeleton diagram of the degassing extruding device of expression one embodiment of the present of invention
Fig. 2 is the internal structure skeleton diagram of the degassing extruding device of expression one embodiment of the present of invention
Fig. 3 is the manufacturing installation pie graph of (methyl) acrylic polymer of expression one embodiment of the present of invention
[symbol description]
10. polymeric kettle
11. agitating device
12. feedstock composition input port
13. reactant mixture outlet
20. connecting portion.
21. pump
22. heater
23～25. pipe arrangements
40. degassing extruding device
41. reactant mixture supply port
42.43. outlet
44. polymer outlet
46. shaft sealing
47. screw rod
48. ring
49. additive input port
50. the threaded shank of reverse propulsion
51. ring
The specific embodiment
[embodiment]
Below, describe the present invention in detail with embodiment.
[embodiment 1]
In being provided with the slot type reaction unit (polymeric kettle) of agitating device, drop into by following match ratio raw materials mixed composition, under 135 ℃ of design temperatures, 3 hours reaction condition of mean residence time, carry out polymerisation.
＜feedstock composition 〉
Methyl methacrylate (MMA) 98.0 mass parts
Methyl acrylate (MA) 2.0 mass parts
N-octyl mercaptan 0.25 mass parts
Tert-butyl hydroperoxide _ 3,5, the own ester of 5, one trimethyls
(MMA and MA are added up to total amount) 70ppm (quality)
Reactant mixture from the extraction of slot type reaction unit, after in the heater of forming by multi tube heat exchanger, being heated to 220 ℃, import in single screw rod degassing extruding device (Φ 150mm, screw rod L/D28) of structure as shown in Figure 1, processing pressure-the 0.097MPa (gauge pressure) of outlet pressure-0.02MPa (gauge pressure) of 42, outlet 43 [260 ℃ ,] that outgases obtains (methyl) acrylic polymer.In addition, from the additive input port of degassing extruding device, drop into the releasing agent (trade name: カ Le コ one Le 8688 flower Wang She systems) of the 2000ppm amount that all is mixed in (methyl) acrylic polymer.
Turned round continuously 7, the demoulding dosage that has still obtained being contained in (methyl) acrylic polymer is 2000ppm all the time.In addition, confirm, do not contain releasing agent in the volatilization composition that the degassing is removed through gas-chromatography.
[reference examples 1]
Except that the screw rod that inserts is not established ring 48, adopt single screw rod degassing extruding device (Φ 150mm, screw rod L/D28) of structure shown in Figure 1, operation similarly to Example 1 makes (methyl) acrylic polymer.
Continuously running obtained on the 7th is contained in demoulding dosage average out to 1900ppm in (methyl) acrylic polymer.In addition, confirm, contain releasing agent in the volatilization composition that the degassing is removed through gas-chromatography.
Claims (5)
1. degassing extruding device has
Can supply with the reactant mixture contain polymer and volatilization composition the reactant mixture supply port and
Can discharge the described polymer of separating from this reactant mixture the polymer outlet and
Can discharge one or more outlets of the described volatilization composition of separating from this reactant mixture and revolvable screw rod and
With compare in set above-mentioned exit position, the most close above-mentioned polymer outlet position, the position that more close above-mentioned polymer is discharged oral-lateral is provided with the additive input port.
It is characterized in that,
Be arranged on the described outlet of position, the most close described additive input port the position, and be provided with between the position, described additive input port, further have and make the temporary transient structure that stops of described polymer.
2. degassing extruding device according to claim 1 makes the temporary transient structure that stops of described polymer, is the ring that is arranged on the described screw rod.
3. degassing extruding device according to claim 1 makes the temporary transient structure that stops of described polymer, is the threaded shank that is arranged at the reverse propulsion on the described screw rod.
4. the manufacturing installation of (methyl) acrylic polymer is provided with each described degassing extruding device, polymeric kettle and the connecting portion that is connected this polymeric kettle and this degassing extruding device of claim 1～3.
5. the manufacture method of (methyl) acrylic polymer, it has
(A) the feedstock composition that contains (methyl) acrylic monomer, free radical polymerization initiator and chain-transferring agent supply with continuously polymeric kettle operation and
(B) in this polymeric kettle, make the polymerization of described (methyl) acrylic monomer at least a portion, make contain above-mentioned (methyl) acrylic monomer at least a portion polymerization (methyl) acrylic polymer the reactant mixture operation and
(C) this reactant mixture from the operation of described polymeric kettle continuous drawing and
(D) the described reactant mixture that extracts from described polymeric kettle, each the described degassing extruding device that imports claim 1～3 outgas the operation handled and
(E) drop into the operation of additive from described additive input port.
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| JP2003344553 | 2003-10-02 | ||
| JP2003344553A JP2005112869A (en) | 2003-10-02 | 2003-10-02 | Devolatilizing extrusion apparatus, and manufacturing apparatus of (meth)acrylic polymer and manufacturing method of (meth)acrylic polymer using the same |
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| CN1618591A CN1618591A (en) | 2005-05-25 |
| CN100448639C true CN100448639C (en) | 2009-01-07 |
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| CN106661145A (en) * | 2014-08-06 | 2017-05-10 | 株式会社可乐丽 | Method for producing (meth)acrylic resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5029493B2 (en) * | 2008-05-26 | 2012-09-19 | 日立電線株式会社 | Method for separating and recycling a mixture of a polymer compound and a gaseous substance, a method for producing an electric wire / cable provided with a recycled coating material, and a separation and recycling apparatus |
| JP5247314B2 (en) * | 2008-09-03 | 2013-07-24 | 三菱レイヨン株式会社 | Methacrylic resin composition |
| JP5230363B2 (en) * | 2008-11-05 | 2013-07-10 | 株式会社日本触媒 | Method for producing thermoplastic resin composition |
| JP4995948B2 (en) * | 2010-07-08 | 2012-08-08 | 住友化学株式会社 | Devolatilizing extruder, devolatilizing extrusion method for polymer composition using the same and methacrylic polymer production method |
| JP5621836B2 (en) * | 2012-12-13 | 2014-11-12 | 三菱レイヨン株式会社 | Methacrylic resin composition |
| JP5672321B2 (en) * | 2013-03-07 | 2015-02-18 | 三菱レイヨン株式会社 | Methacrylic resin composition |
| JP5619239B1 (en) * | 2013-08-27 | 2014-11-05 | 株式会社日本製鋼所 | Bent type twin-screw kneading extrusion apparatus and method |
| WO2020085474A1 (en) * | 2018-10-26 | 2020-04-30 | 株式会社クラレ | Method for producing methacrylic resin composition |
| CN110774554A (en) * | 2019-12-13 | 2020-02-11 | 泰兴汤臣压克力有限公司 | One-time reaction extrusion molding production line for acrylic plates |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238785A (en) * | 1996-07-25 | 1999-12-15 | 三菱丽阳株式会社 | Process for the prepration of poly(meth) acrylic acid ester |
| CN1303397A (en) * | 1998-07-14 | 2001-07-11 | 三菱丽阳株式会社 | Process for producing metha crylic polymer |
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| JPS5043166A (en) * | 1973-08-22 | 1975-04-18 | ||
| JP4105814B2 (en) * | 1999-01-19 | 2008-06-25 | 東洋スチレン株式会社 | Method for producing thermoplastic resin composition |
| JP3746998B2 (en) * | 2001-01-22 | 2006-02-22 | 株式会社クラレ | Process for producing ethylene-vinyl alcohol copolymer resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238785A (en) * | 1996-07-25 | 1999-12-15 | 三菱丽阳株式会社 | Process for the prepration of poly(meth) acrylic acid ester |
| CN1303397A (en) * | 1998-07-14 | 2001-07-11 | 三菱丽阳株式会社 | Process for producing metha crylic polymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661145A (en) * | 2014-08-06 | 2017-05-10 | 株式会社可乐丽 | Method for producing (meth)acrylic resin composition |
| CN106661145B (en) * | 2014-08-06 | 2019-04-09 | 株式会社可乐丽 | The manufacturing method of (methyl) acrylic resin composition |
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| JP2005112869A (en) | 2005-04-28 |
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