WO2020256018A1 - Method for producing acrylic rubber - Google Patents
Method for producing acrylic rubber Download PDFInfo
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- WO2020256018A1 WO2020256018A1 PCT/JP2020/023789 JP2020023789W WO2020256018A1 WO 2020256018 A1 WO2020256018 A1 WO 2020256018A1 JP 2020023789 W JP2020023789 W JP 2020023789W WO 2020256018 A1 WO2020256018 A1 WO 2020256018A1
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- WIPO (PCT)
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- acrylic rubber
- extruder
- vent port
- decompression
- absolute pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/02—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of crude rubber, gutta-percha, or similar substances
- B29B15/06—Washing devices
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
Definitions
- the present invention relates to a method for producing acrylic rubber, and more particularly to a method for producing acrylic rubber that can appropriately reduce the water content of acrylic rubber while suppressing the occurrence of vent-up.
- Acrylic rubber is widely used for functional parts mainly for automobile applications as a rubber material from which a crosslinked rubber product having excellent properties such as heat resistance and compression set resistance can be obtained. Further, in the process of producing acrylic rubber, a process of salting out the rubber polymer and then extruding and drying it with an extruder or the like is performed.
- Patent Document 1 in a technique of extruding and drying a rubber polymer by an extruder or the like, a vent port that communicates with atmospheric pressure to depressurize and discharge the vaporized material to the atmosphere and a vent port that forcibly depressurizes and discharges the vaporized material
- Patent Document 1 an extruder having a plurality of decompression vent ports is exemplified, but no mention is made as to what condition the absolute pressure of the plurality of decompression vent ports should be.
- Patent Document 2 discloses a technique for extruding and drying a rubber polymer by an extruder or the like, in which the extruded rubber polymer is further dried by a sealed steam flow.
- various conditions such as the amount of rubber polymer extruded from the tip of the extruder, the number of rotations of the screw of the extruder, the pressure of the polymer inside the tip of the extruder, and the specific energy of the extruder. The experimental results when the above is changed are disclosed.
- Patent Documents 3 and 4 unlike the techniques of only dehydrating and drying the rubber polymer in the extruder as in Patent Document 1 and Patent Document 2, the salting of the rubber polymer and the salting of the rubber polymer in the extruder are provided. Following this, techniques for dehydration and drying are disclosed.
- Patent Documents 3 and 4 an embodiment in which an extruder having a plurality of vent ports is used as an extruder is exemplified, but also in Patent Documents 3 and 4, the absolute pressure of the plurality of vent ports is set as any condition. No mention is made of this.
- the acrylic rubber is dehydrated and dried in this order.
- Drying following dehydration is usually performed by vacuum drying through a vacuum vent port.
- molten acrylic rubber foams at the decompression vent port, causing vent-up in which the acrylic rubber flows into the decompression vent port, which reduces productivity. There was a problem that it would end up.
- the present invention has been made in view of such an actual situation, and an object of the present invention is to provide a method for producing acrylic rubber, which can appropriately reduce the water content of acrylic rubber while suppressing the occurrence of vent-up. ..
- the present inventors have used an extruder having a plurality of pressure reducing vent ports when drying acrylic rubber, and extruded the acrylic rubber.
- the above object can be achieved by making the absolute pressure of the decompression vent port on the upstream side in the direction higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction, and have completed the present invention.
- it is a method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which screws are rotatably arranged inside a barrel.
- an extruder one having a plurality of decompression vent ports was used.
- a method for producing acrylic rubber in which the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is made higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
- the difference between the absolute pressure of the decompression vent port on the upstream side in the extrusion direction and the absolute pressure of the decompression vent port on the downstream side in the extrusion direction is preferably in the range of 5.0 to 94.0 kPa.
- the extruder having two or more decompression vent ports is used, and the absolute pressures of at least two decompression vent ports among the two or more decompression vent ports are extruded from the upstream side in the extrusion direction. It is preferable to set it so that it becomes lower in order toward the downstream side in the direction. In the present invention, it is preferable to use an extruder having a plurality of viewing windows at the plurality of pressure reducing vent ports.
- the acrylic rubber is put into the extruder in a hydrous crumb state to dry the acrylic rubber.
- the acrylic rubber is put into the extruder in a crumb state having a water content of 60 to 70% by weight to dry the acrylic rubber.
- the extruder provided with a first discharge slit and a second discharge slit in order from the upstream side in the extrusion direction on the upstream side in the extrusion direction from the plurality of pressure reducing vent ports.
- the processing amount of acrylic rubber dried by the extruder per unit time is Q [kg / h] and the rotation speed of the screw is N [rpm]
- the following formula (1) is satisfied. Is preferable. 3 ⁇ Q / N ⁇ 8 (1)
- a cleaning step of cleaning the acrylic rubber is further provided in the cleaning tank, and the cleaning step and the drying step are continuous steps in this order.
- a method for producing an acrylic rubber which can appropriately reduce the water content of the acrylic rubber while suppressing the occurrence of vent-up.
- FIG. 1 is a schematic view showing a cleaning tank and an extruder used in the method for producing acrylic rubber according to the embodiment of the present invention.
- FIG. 2 is a schematic view showing a screw arranged inside the extruder.
- FIG. 3 is a cross-sectional view taken along the line III-III of FIG. 1 and the line III-III of FIG.
- the method for producing acrylic rubber of the present invention is a method for producing acrylic rubber, which comprises a drying step of drying the acrylic rubber using an extruder in which screws are rotatably arranged inside a barrel.
- an extruder one having a plurality of decompression vent ports was used.
- the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is set higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
- the acrylic rubber used in the production method of the present invention has a (meth) acrylic acid ester monomer as a main component (preferably having 30% by weight or more in the total rubber monomer unit) in the molecule.
- Acrylic acid ester monomer and / or methacrylic acid ester monomer are a rubber-like polymer containing a unit.
- the (meth) acrylic acid ester monomer forming the (meth) acrylic acid ester monomer unit which is the main component of the acrylic rubber used in the production method of the present invention is not particularly limited, but for example, (meth) acrylic.
- examples thereof include an acid alkyl ester monomer and a (meth) acrylic acid alkoxyalkyl ester monomer.
- the (meth) acrylic acid alkyl ester monomer is not particularly limited, but an ester of alkanol having 1 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, methyl (meth) acrylic acid, ( Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) Examples thereof include 2-ethylhexyl acrylate and cyclohexyl (meth) acrylate.
- (meth) acrylic acid alkyl ester monomer having an alkyl group having 2 or more carbon atoms is preferable
- ethyl (meth) acrylate and n-butyl (meth) acrylic acid are more preferable
- acrylic acid is particularly preferred. These can be used alone or in combination of two or more.
- the (meth) acrylic acid alkoxyalkyl ester monomer is not particularly limited, but an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, (meth) acrylic acid.
- 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable, and 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly preferable. These can be used alone or in combination of two or more.
- the (meth) acrylic acid ester monomer unit includes 30 to 100% by weight of the (meth) acrylic acid alkyl ester monomer unit, and the (meth) acrylic acid alkoxyalkyl ester. It is preferable to use a monomer unit consisting of 70 to 0% by weight.
- the content of the (meth) acrylic acid ester monomer unit in the acrylic rubber used in the production method of the present invention is preferably 30% by weight or more, more preferably 50 to 99.9% by weight, still more preferably. It is 80 to 99.5% by weight, particularly preferably 95 to 99.5% by weight. If the content of the (meth) acrylic acid ester monomer unit is too small, the weather resistance, heat resistance, and oil resistance of the obtained rubber crosslinked product may decrease, while if it is too large, the obtained rubber crosslinked product may be deteriorated. The mechanical strength of the object may decrease.
- the acrylic rubber used in the production method of the present invention may contain a crosslinkable monomer unit in addition to the (meth) acrylic acid alkyl ester monomer unit, if necessary.
- the crosslinkable monomer forming the crosslinkable monomer unit is not particularly limited, and is, for example, an ⁇ , ⁇ -ethylene unsaturated carboxylic acid monomer; a monomer having an epoxy group; having a halogen atom. Monomer; diene monomer; and the like.
- the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer forming the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer unit is not particularly limited, and is, for example, ⁇ , ⁇ - having 3 to 12 carbon atoms.
- the acrylic rubber can be made into a carboxyl group-containing acrylic rubber having a carboxyl group as a cross-linking point, whereby a rubber cross-linked product can be obtained. , The compression resistance and permanent strain resistance can be further improved.
- ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, and cinnamic acid.
- Specific examples of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butendioic acids such as fumaric acid and maleic acid; itaconic acid; citraconic acid; chloromaleic acid; and the like.
- monoester of ⁇ , ⁇ -ethylenic unsaturated dicarboxylic acid having 4 to 12 carbon atoms and alkanol having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, and malein.
- Itaconic acid monochain alkyl esters such as monomethyl acid, monoethyl maleate, monon-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, maleine
- examples thereof include butenedioic acid monoesters having an alicyclic structure such as monocyclohexenyl acid acid; itaconic acid monoesters such as monomethyl itaconic acid, monoethyl itaconic acid, monon-butyl itaconic acid, and monocyclohexyl itaconic acid.
- a monoester of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkanol having 1 to 8 carbon atoms is preferable, and a monoester of butendioic acid or butendion having an alicyclic structure Acid monoesters are more preferred, mono-n-butyl fumarate, mono n-butyl maleate, monocyclohexyl fumarate, and monocyclohexyl maleate are even more preferred, and mono n-butyl fumarate is particularly preferred.
- These ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more.
- the dicarboxylic acid also includes those existing as anhydrides.
- the monomer having an epoxy group is not particularly limited, and for example, an epoxy group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate; an epoxy group-containing ether such as allyl glycidyl ether and vinyl glycidyl ether; Can be mentioned.
- the monomer having a halogen atom is not particularly limited, and for example, an unsaturated alcohol ester of a halogen-containing saturated carboxylic acid, a (meth) acrylic acid haloalkyl ester, a (meth) acrylic acid haloacyloxyalkyl ester, or (meth) acrylic.
- an unsaturated alcohol ester of a halogen-containing saturated carboxylic acid a (meth) acrylic acid haloalkyl ester, a (meth) acrylic acid haloacyloxyalkyl ester, or (meth) acrylic.
- acrylic include acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers.
- unsaturated alcohol esters of halogen-containing saturated carboxylic acids include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
- Specific examples of the (meth) acrylic acid haloalkyl ester include chloromethyl (meth) acrylic acid, 1-chloroethyl (meth) acrylic acid, 2-chloroethyl (meth) acrylic acid, and 1,2-dichloroethyl (meth) acrylic acid. , 2-Chloropropyl (meth) acrylic acid, 3-chloropropyl (meth) acrylic acid, and 2,3-dichloropropyl (meth) acrylic acid.
- (meth) acrylic acid haloacyloxyalkyl ester examples include (meth) acrylic acid 2- (chloroacetoxy) ethyl, (meth) acrylic acid 2- (chloroacetoxy) propyl, and (meth) acrylic acid 3- (chloro). Examples thereof include acetoxy) propyl and 3- (hydroxychloroacetoxy) propyl (meth) acrylate.
- (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl ester examples include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylic acid and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylic acid. Can be mentioned.
- halogen-containing unsaturated ether examples include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether and the like.
- halogen-containing unsaturated ketone examples include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone and the like.
- halomethyl group-containing aromatic vinyl compound examples include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl- ⁇ -methylstyrene.
- halogen-containing unsaturated amide examples include N-chloromethyl (meth) acrylamide.
- haloacetyl group-containing unsaturated monomer examples include 3- (hydroxychloroacetoxy) propylallyl ether and p-vinylbenzylchloroacetic acid ester.
- Examples of the diene monomer include a conjugated diene monomer and a non-conjugated diene monomer.
- Specific examples of the conjugated diene monomer include 1,3-butadiene, isoprene, and piperylene.
- Specific examples of the non-conjugated diene monomer include ethylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate. ..
- the acrylic rubber when an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer is used, the acrylic rubber can be a carboxyl group-containing acrylic rubber.
- a carboxyl group-containing acrylic rubber as the acrylic rubber, it is possible to improve the compression resistance and permanent strain resistance while improving the oil resistance and heat resistance.
- the content of the crosslinkable monomer unit in the acrylic rubber used in the production method of the present invention is preferably 0.01% by weight or more, more preferably 0.1 to 50% by weight, still more preferably 0. It is 5 to 20% by weight, particularly preferably 0.5 to 5% by weight.
- the acrylic rubber used in the production method of the present invention is, in addition to the (meth) acrylic acid ester monomer unit and the crosslinkable monomer unit used as needed, other monomers copolymerizable with these. It may have a unit of.
- Other such copolymerizable monomers include aromatic vinyl monomers, ⁇ , ⁇ -ethylenic unsaturated nitrile monomers, acrylamide-based monomers, and ⁇ , ⁇ -ethylenic unsaturated dicarboxylics. Examples thereof include acid diester monomers and other olefin-based monomers.
- aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, and divinylbenzene.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
- Examples of the acrylamide-based monomer include acrylamide and methacrylamide.
- the ⁇ , ⁇ -ethylenic unsaturated dicarboxylic acid diester monomer is a maleic acid dialkyl ester such as dimethyl maleate or din-butyl maleate having an alkyl group having 1 to 18 carbon atoms; fumaric acid.
- a fumaric acid dialkyl ester such as dimethyl or din-butyl fumarate having an alkyl group having 1 to 18 carbon atoms; a dicyclopentyl maleate such as dicyclopentyl maleate or dicyclohexyl maleate and a cycloalkyl ester.
- a group having 4 to 16 carbon atoms a dicycloalkyl ester of fumaric acid such as dicyclopentyl fumarate and dicyclohexyl fumarate having a cycloalkyl group having 4 to 16 carbon atoms; dimethyl itaconate, di-itaconate Itaconic acid dialkyl ester such as n-butyl having an alkyl group having 1 to 18 carbon atoms: an itaconic acid dicycloalkyl ester such as dicyclohexyl itaconate having a cycloalkyl group having 4 to 16 carbon atoms. ; And so on.
- olefin-based monomers include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, ethyl vinyl ether, and butyl vinyl ether.
- styrene, acrylonitrile, methacrylonitrile, ethylene and vinyl acetate are preferable, and acrylonitrile, methacrylonitrile, and ethylene are more preferable.
- copolymerizable monomers can be used alone or in combination of two or more.
- the content of the unit of these other copolymerizable monomers in the acrylic rubber of the present invention is usually 49.9% by weight or less, preferably 19.5% by weight or less, and more preferably 10% by weight or less. , More preferably 4.5% by weight or less.
- the content may be in the above range.
- the content of ethylene units is preferably 10% by weight or less, and more preferably 4.5% by weight or less.
- the acrylic rubber used in the production method of the present invention has an acrylonitrile unit or a methacrylonitrile unit, the total content of the acrylonitrile unit and the methacrylonitrile unit shall be 10% by weight or less. It is preferable to use 4.5% by weight or less.
- the acrylic rubber used in the production method of the present invention is preferably obtained by polymerizing each of the above monomers.
- any of an emulsion polymerization method, a suspension polymerization method, a massive polymerization method, and a solution polymerization method can be used, but from the viewpoint of ease of control of the polymerization reaction, known acrylic rubber It is preferable to use an emulsion polymerization method or a solution polymerization method under normal pressure, which is generally used as a production method.
- acrylic rubber is obtained in the form of latex (latex of acrylic rubber).
- acrylic rubber can be obtained in the form of a polymer solution (polymer solution of acrylic rubber).
- the polymerization may be a batch type, a semi-batch type, or a continuous type.
- the polymerization is usually carried out in a temperature range of 0 to 70 ° C, preferably 5 to 50 ° C.
- Acrylic rubber hydrous crumb specifically, a mixture of acrylic rubber crumb and serum water (hereinafter referred to as "clam slurry") can be obtained.
- the serum water means water that may contain a coagulant, a polymerization auxiliary material residue, or the like (a coagulant, a polymerization auxiliary material residue, or the like may be dissolved or dispersed).
- serum water either the water associated with the acrylic rubber crumb or the water accompanying the acrylic rubber crumb and later separated is defined as serum water.
- the serum water is used including the case where the type and amount of the dissolved or dispersed components are changed due to washing or drying.
- the coagulant include calcium chloride, magnesium chloride, sodium chloride, magnesium sulfate, barium chloride and the like.
- FIG. 1 is a schematic view showing a cleaning tank and an extruder used in the method for producing acrylic rubber according to the embodiment of the present invention.
- the washing tank and the extruder according to the embodiment shown in FIG. 1 are used as the manufacturing apparatus used in the method for manufacturing the acrylic rubber of the present invention
- emulsion polymerization or solution polymerization will be carried out as described above.
- the crumb slurry (more specifically, the water-containing crumb contained in the crumb slurry) obtained by solidification is washed and then dried to obtain a solid acrylic rubber. The method will be described.
- the manufacturing apparatus includes an extruder 1 and a cleaning tank 7.
- the crumb slurry obtained according to the above method is continuously supplied to the washing tank 7, and the water-containing crumb contained in the crumb slurry is washed in the washing tank 7.
- the washed clam slurry (more specifically, the clam slurry containing the washed hydrous crumb) is continuously discharged from the washing tank 7, and the continuously discharged clam slurry (more specifically).
- the clam slurry containing the washed hydrous crumb is continuously supplied to the feed port 310 of the extruder 1 from the discharge port provided in the washing tank 7.
- the washed crumb slurry is continuously discharged from the discharge port provided in the washing tank 7 and passes through the water removal facility 8 (for example, draining by a screen) shown in FIG.
- the water removal facility 8 for example, draining by a screen
- the feed port 310 of the extruder 1 After some water has been removed, it is continuously supplied to the feed port 310 of the extruder 1 in the state of a hydrous crumb (that is, the state of a crumb containing water) or the state of a crumb slurry. It has become. If it is in the state of a hydrous crumb, it may be accompanied by water.
- the hydrous crumb or the crumb slurry supplied to the feed port 310 of the extruder 1 is dried in the extruder 1 as described later.
- cleaning by the cleaning tank 7 and drying by the extruder 1 are performed in a continuous process, so that space saving and improvement of production efficiency are possible. Furthermore, it is possible to improve the production stability by performing it in a continuous process
- the method for cleaning the clam slurry (more specifically, the water-containing crumb contained in the clam slurry) by the cleaning tank 7 is not particularly limited, but the cleaning tank 7 is supplied with cleaning water together with the clam slurry for cleaning.
- a method of stirring by a stirring blade provided in the tank 7 can be mentioned.
- the amount of washing water supplied with respect to 100 parts by weight of the crumb is preferably 900 to 9900 parts by weight, more preferably 1570 to 4900 parts by weight, from the viewpoint of effectively performing washing.
- the embodiment in which one cleaning tank 7 is provided is illustrated in FIG. 1, the embodiment in which two or more cleaning tanks are provided in multiple stages may be configured to perform cleaning a plurality of times.
- the extruder 1 has a drive unit 2 and a single barrel 3 composed of 11 divided barrel blocks 31 to 41. Inside the barrel 3, a supply zone 100, a dehydration zone 102, and a drying zone 104 are sequentially formed from the upstream side to the downstream side of the barrel 3.
- the supply zone 100 is a region for supplying the hydrous crumb or the crumb slurry continuously supplied from the cleaning tank 7 to the inside of the barrel 3.
- the dehydration zone 102 is a region for separating and discharging a liquid (serum water) containing a coagulant or the like from the hydrous crumb or crumb slurry.
- the drying zone 104 is a region for drying the dehydrated crumbs.
- the inside of the barrel block 31 corresponds to the supply zone 100
- the inside of the barrel blocks 32 to 34 corresponds to the dehydration zone 102
- the inside of the barrel blocks 35 to 41 corresponds to the drying zone 104.
- the number of barrel blocks installed can be optimized according to the composition of the acrylic rubber to be handled, and is not limited to the mode shown in FIG.
- a feed port 310 for receiving a water-containing crumb or a crumb slurry was formed in the barrel block 31 constituting the supply zone 100, and a part of water was removed from the washing tank 7 through the screen 8 in the feed port 310. , Hydrous crumbs or crumb slurries are continuously fed. Further, the barrel blocks 32 and 34 forming the dehydration zone 102 are formed with a first discharge slit 320 and a second discharge slit 340 for draining the water contained in the water-containing crumb, respectively. Further, in the barrel blocks 36, 38, 39, 40 which form a part of the drying zone 104, the first decompression vent port 360 for removing volatile substances such as water contained in the crumb after dehydration by degassing. , The second decompression vent port 380, the third decompression vent port 390, and the fourth decompression vent port 400 are formed, respectively.
- FIG. 2 is a schematic view showing a screw arranged inside the extruder 1.
- a screw 6 as shown in FIG. 2 is arranged inside the barrel 3.
- a drive means such as a motor housed in a drive unit 2 (see FIG. 1) is connected to the base end of the screw 6 in order to drive the screw 6, whereby the screw 6 is rotatably held. ..
- the shape of the screw 6 is not particularly limited, but it is preferable to appropriately combine a screw block having various screw configurations and a kneading disc.
- the screw 6 can be configured to have different screw configurations in the regions corresponding to the zones 100, 102, and 104 described above formed inside the barrel 3.
- the L / Da is preferably 20 to 60. Is.
- the outer diameter Da of the screw 6 is defined by the diameter of the peak portion 60A (see FIG. 3) of the screw block 60 constituting the screw when viewed from the axial direction.
- FIG. 3 is a cross-sectional view taken along the lines III-III of FIG. 1 and the line III-III of FIG. 2, and the cross-sectional view shown in FIG. 3 is a cross-sectional view of the screw block 60 portion of the extruder 1. It is sectional drawing which crosses the valley part 60B. That is, as shown in FIG. 3, the two screws 6 and 6 mesh the peak portion 60A of the screw block 60 of one screw 6 with the valley portion 60B of the screw block 60 of the other screw 6 and one of them.
- the mixing property in each zone 100, 102, 104 can be improved.
- the rotation directions of the two screws 6 may be the same direction or different directions, but from the viewpoint of self-cleaning performance, a type that rotates in the same direction is preferable.
- Da / Di is preferable. Is in the range of 1.2 to 2.5.
- the relationship between L1 and the entire length of the screw 6 described above is L (mm) L1.
- / L is preferably 0.2 to 0.9.
- a die 5 for extruding the acrylic rubber dehydrated and dried in the barrel 3 into a predetermined shape and commercializing it is connected to the downstream side of the barrel block 41 described above, for example, drying.
- the acrylic rubber can be extruded into a sheet.
- the crumb slurry washed by the washing tank 7 is passed through a water removing facility 8 (for example, draining with a screen) to remove a part of water, and the acrylic rubber crumb is used. Is continuously supplied to the feed port 310 provided in the barrel block 31 in the state of a water-containing crumb or a crumb slurry in which a part of water has been removed.
- the clam slurry washed by the washing tank 7 is continuously supplied from the washing tank 7 directly (or via a predetermined clam slurry flow path) to the feed port 310 provided in the barrel block 31. May be good.
- the amount of the coagulant contained in the finally obtained dried acrylic rubber can be suppressed to a low level, and From the viewpoint of reducing the slipping out of the crumb from the first discharge slit 320, which will be described later, it is preferable that the water content is relatively high.
- the water content of the crumb supplied to the feed port 310 is , It is preferably 50 to 70% by weight, more preferably 58 to 70% by weight, and even more preferably 60 to 70% by weight.
- the water content of the clam supplied to the feed port 310 includes, for example, the water content of the clam slurry before cleaning supplied to the cleaning tank 7, the amount of cleaning water supplied to the cleaning tank 7, and water such as a slit screen. It can be controlled by adjusting through the removal equipment 8.
- the average crumb diameter of the crumb-shaped acrylic rubber contained in the hydrous crumb or the crumb slurry supplied to the feed port 310 is not particularly limited, but is preferably 0.1 to 10 mm from the viewpoint of improving the drying efficiency. , More preferably 1.0 to 5.0 mm.
- the average crumb diameter of the crumb-shaped acrylic rubber can be controlled by adjusting the solidification conditions at the time of solidification.
- the temperature of the hydrous crumb or the crumb slurry supplied to the feed port 310 is preferably 30 to 90 ° C., more preferably 40 to 90 ° C., still more preferably 50 to 85, from the viewpoint of ensuring sufficient drying efficiency. °C.
- the temperature of the hydrous crumb or crumb slurry supplied to the feed port 310 is the polymerization temperature of acrylic rubber, the temperature of the coagulant used for coagulation (for example, the temperature of the coagulant aqueous solution), and the temperature of the washing water when washing by the washing tank 7. It can be controlled by adjusting such as.
- the barrel temperature in the barrel block 31 constituting the supply zone 100 is not particularly limited, but is preferably 30 to 150 ° C., more preferably 40 to 140 ° C. from the viewpoint of improving the drying efficiency while suppressing the deterioration of the acrylic rubber. Is.
- the hydrous crumb or crumb slurry supplied to the feed port 310 is sent from the supply zone 100 to the dehydration zone 102 by the rotation of the screw 6.
- the water-containing crumb or serum water contained in the crumb slurry (more specifically, more specifically, (Serum water separated from the crumbs) is discharged to obtain a hydrous crumb in a state of preferably containing 10 to 50% by weight of water, more preferably 10 to 40% by weight of water. Can be done.
- the barrel temperature in the barrel blocks 32 to 34 constituting the dehydration zone 102 is not particularly limited, but is preferably 30 to 170 ° C., more preferably 40 to 170 ° C. from the viewpoint of increasing the dehydration efficiency while suppressing the deterioration of the acrylic rubber. It is 160 ° C.
- the water-containing crumb obtained in the dehydration zone 102 is sent to the drying zone 104 by the rotation of the screw 6.
- the crumb sent to the drying zone 104 is plasticized and kneaded by the rotation of the screw 6 to form a melt, which generates heat and is carried to the downstream side while raising the temperature.
- the melt reaches the decompression vent ports 360, 380, 390, 400 provided in the barrel blocks 36, 38, 39, 40, the pressure is released, so that the moisture contained in the melt is released. Volatile matter is separated and vaporized.
- the decompression vent ports 360, 380, 390, and 400 are connected to a decompression pump via a decompression pipe connected to the side surface of each decompression vent port so that the pressure is reduced. It is configured in. Further, the decompression vent ports 360, 380, 390, and 400 are provided with a valve (not shown) for adjusting the absolute pressure and a pressure gauge (not shown) for measuring the absolute pressure. The absolute pressure can be adjusted. In addition, in FIG. 1, the decompression vent ports 360, 380, 390, and 400 are illustrated as being connected to the same decompression pump through a decompression pipe, but the present invention is not particularly limited to such an embodiment and is separate. May be connected to a decompression pump.
- the absolute of the fourth vacuum vent 400 positioned absolute pressure P 1 of the first vacuum vent port 360 which is located on the most upstream side of the vacuum vent port 360,380,390,400, on the most downstream side It shall be higher than the pressure P 4 (P 1 > P 4 ).
- the absolute pressure P 1 of the first decompression vent port 360 may be higher than the absolute pressure P 4 of the fourth decompression vent port 400 (P 1 > P 4 ) (that is, the most upstream).
- the absolute pressure of the decompression vent port on the side may be higher than the absolute pressure of the decompression bend port on the most downstream side), and the difference between these pressures shall be in the range of 5.0 to 94.0 kPa.
- the range is preferably 9.0 to 92.0 kPa, more preferably 18.0 to 88.0 kPa.
- the absolute pressure P 1 of the first decompression vent port 360 represents the absolute pressure of the most upstream decompression vent port
- the absolute pressure P 4 of the fourth decompression vent port 400 is the most downstream decompression vent port. Represents the absolute pressure of.
- the absolute pressure P 1 of the first decompression vent port 360 may be higher than the absolute pressure P 4 of the fourth decompression vent port 400 (P 1 > P 4 ).
- the absolute pressure of the decompression vent port is not particularly limited, but the absolute pressure of the first decompression vent port 360 is preferably 7.3 to 96.3 kPa, more preferably 11.3 to 94.3 kPa. It is more preferably 21.3 to 91.3 kPa.
- an absolute pressure P 1 of the first vacuum vent port 360 as long as greater than the absolute pressure P 4 of the fourth vacuum vent 400, the absolute of the second vacuum vent port 380
- the absolute pressure of each decompression vent port may be appropriately set so as to have the above relationship, and is not particularly limited, but the absolute pressure of the second decompression vent port 370 is preferably 2.3 to 91.3 kPa. It is more preferably 6.3 to 81.3 kPa, and even more preferably 11.3 to 71.3 kPa.
- the absolute pressure of the third decompression vent port 380 is preferably 2.3 to 61.3 kPa, more preferably 3.3 to 51.3 kPa, and 3.3 to 46.3 kPa.
- the absolute pressure of the fourth decompression vent port 400 is preferably 2.3 to 51.3 kPa, more preferably 3.3 to 41.3 kPa, and 3.3 to 36.3 kPa. It is more preferable to do so.
- the absolute pressure of the fourth decompression vent port 400 when relatively low, preferably 2.3 to 21.3 kPa, more preferably 2.3 to 11.3 kPa, the first decompression vent the absolute pressure P 1 of the mouth 360, the difference in pressure between the absolute pressure P 4 of the fourth vacuum vent 400, preferably in the range of 60 ⁇ 94.0kPa, more preferably 70 ⁇ 94.0kPa, further It is preferably 80 to 88.0 kPa.
- the absolute pressure of the fourth decompression vent port 400 is relatively high, preferably 22.3 to 51.3 kPa, more preferably 26.3 to 41.3 kPa, and even more preferably 28.3 to 36.3 kPa.
- the absolute pressure P 1 of the first vacuum vent port 360 that the difference in pressure between the absolute pressure P 4 of the fourth vacuum vent port 400, in the range of 5.0 ⁇ 25 kPa preferably , More preferably 5.0 to 20 kPa, still more preferably 7.0 to 15 kPa.
- glass viewing windows 361, 381, 391, 401 are formed on the upper surfaces of the decompression vent ports 360, 380, 390, and 400 so that the inside of the decompression vent can be confirmed. This makes it easy to confirm the presence or absence of vent-up, and even if vent-up occurs at a stage where the operating conditions are not stable, such as at the beginning of operation, such vent-up will occur in a timely manner. Can be found.
- the barrel temperature in the barrel blocks 35 to 41 constituting the drying zone 104 is not particularly limited, but volatile components such as water contained in the acrylic rubber melt while appropriately suppressing the vent-up of the acrylic rubber melt. From the viewpoint that the removal efficiency of the rubber can be further improved, the temperature is preferably 100.0 to 220.0 ° C, more preferably 105.0 to 210.0 ° C.
- the crumb from which the water has passed through the drying zone 104 is sent out to the outlet side by the screw 6, and is in a state of substantially containing almost no water, specifically, the water content is preferably 1.0. It is introduced into the die 5 in a state of being reduced to less than% by weight, more preferably 0.1 to 0.8% by weight, where it is discharged, for example, in the form of a sheet, cooled if necessary, and then a sheet cutter ( It is introduced into (not shown) and cut to an appropriate length.
- the processing amount Q of the acrylic rubber to be dried per unit time is the processing amount [kg / kg / kg / kg / of acrylic rubber to be dried in one hour when the extrusion drying process is performed once in the extruder 1. h].
- the rotation speed N of the screw 6 is the rotation speed [rpm] when the screw 6 rotates inside the barrel 3 in 1 minute in the extruder 1.
- Q / N is preferably 3 ⁇ Q / N ⁇ 8, more preferably 3.5 ⁇ Q / N ⁇ 7, still more preferably 4 ⁇ Q / N ⁇ 6, and particularly preferably 4.5 ⁇ .
- Q / N ⁇ 5.5 is preferably 3 ⁇ Q / N ⁇ 8, more preferably 3.5 ⁇ Q / N ⁇ 7, still more preferably 4 ⁇ Q / N ⁇ 6, and particularly preferably 4.5 ⁇ .
- the absolute pressure P 1 of the first vacuum vent port 360 because it is an higher than the absolute pressure P 4 of the fourth vacuum vent 400, a "Q / N" above range Even in the case of, the vent-up can be appropriately suppressed, and thus the effect of setting "Q / N" in the above range, specifically, the acrylic rubber in which the water content is appropriately reduced can be obtained. It is possible to effectively enhance the effect of being able to produce with high productivity.
- the Mooney viscosity (ML1 + 4, 100 ° C.) (polymer Mooney) of the acrylic rubber produced by the production method of the present embodiment is not particularly limited, but is preferably 10 to 80, more preferably 20 to 70, and even more preferably. It is 25 to 60.
- a method for producing acrylic rubber which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
- the extruder one having a plurality of decompression vent ports was used. It is possible to provide a method for producing acrylic rubber in which the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is made higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
- the water content of the acrylic rubber can be appropriately reduced while suppressing the occurrence of vent-up.
- any embodiment may include an aspect in which the absolute pressure is lower than that of the pressure reducing vent port on the side, and the specific embodiment thereof is not particularly limited.
- a method for producing acrylic rubber which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
- a method for producing acrylic rubber can be provided, in which the extruder is provided with a pressure reducing vent port having a viewing window. According to the invention according to the second aspect of the present invention, it is possible to easily confirm the presence or absence of the occurrence of vent-up.
- a method for producing acrylic rubber which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
- a method for producing acrylic rubber in which acrylic rubber is put into the extruder in a crumb state having a water content of 60 to 70% by weight to dry the acrylic rubber.
- the amount of the coagulant contained in the finally obtained dried acrylic rubber can be suppressed to a low level, and the clam slit is removed from the drainage slit. Can be reduced.
- a method for producing acrylic rubber which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
- the method is provided. 3 ⁇ Q / N ⁇ 8 (1) According to the invention according to the fourth aspect of the present invention, it is possible to effectively enhance the effect that acrylic rubber having an appropriately reduced water content can be produced with high productivity.
- a cleaning process that cleans acrylic rubber in the cleaning tank A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel, and the washing step and the drying step are continuous steps. Provided. According to the invention according to the fifth aspect of the present invention, it is possible to save space and improve production efficiency, and further, it is possible to improve production stability.
- ⁇ Synthesis example 1 200 parts of water, 3 parts of sodium lauryl sulfate and 15 parts of ethyl acrylate, 55 parts of n-butyl acrylate, 28 parts of methoxyethyl acrylate in a polymerization reactor equipped with a thermometer, agitator, nitrogen introduction tube and decompression device. And 2 parts of mono-n-butyl fumarate were charged. After that, oxygen was sufficiently removed by repeating degassing and nitrogen substitution under reduced pressure, and then 0.002 parts of sodium formaldehyde sulfoxylate and 0.005 parts of cumene hydroperoxide were added to carry out an emulsion polymerization reaction at normal pressure and normal temperature.
- Acrylic rubber latex was obtained by starting and continuing the reaction until the polymerization conversion rate reached 95%. Next, the obtained latex of acrylic rubber was coagulated with an aqueous calcium chloride solution to obtain a slurry of acrylic rubber (solid content concentration: 32% by weight).
- Example 1 The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using the washing tank 7 and the extruder 1 shown in FIG. 1 to obtain a solid acrylic rubber.
- the supply rate of acrylic rubber to the cleaning tank 7 when cleaning in the cleaning tank 7 is 500 kg / h (supply rate in terms of solid rubber content), and the cleaning water is supplied to the cleaning tank 7. Washing was performed at a rate of 12000 kg / h.
- the acrylic rubber slurry after cleaning is passed through the water removal facility 8 (slit screen) from the cleaning tank 7 as a water content crumb (moisture content: 60% by weight) of the acrylic rubber (a mode in which water is accompanied by the water content crumb).
- the supply rate of 1250 kg / h to the extruder 1 (supply rate in terms of acrylic rubber (that is, the amount of acrylic rubber to be dried Q). ) was supplied at 500 kg / h) and dried by the extruder 1. Further, the temperature of the water-containing crumb of acrylic rubber at the time of charging into the extruder 1 was set to 40 ° C.
- the conditions for drying by the extruder 1 are the barrel temperature of the supply zone 100: 80 ° C., the barrel temperature of the dehydration zone 102: 130 ° C., and the barrel temperature of the drying zone 104: 160 ° C., and the absolute pressure reducing vent port 360 of the first decompression vent port 360.
- absolute pressure of the third decompression vent port 390 4 kPa
- absolute pressure of the fourth decompression vent port 400 4 kPa (first decompression vent).
- the water content of the water-containing crumb after passing through the dehydration zone 102 was 40% by weight.
- the washing tank 7 and the extruder 1 are used to wash the acrylic rubber slurry and dry the water-containing crumb of the acrylic rubber to continuously obtain a solid acrylic rubber for 2 hours continuously.
- vent-up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.7% by weight.
- the Mooney viscosity (ML1 + 4, 100 ° C.) (measured according to JIS K6300-1; the same applies hereinafter) of the obtained solid acrylic rubber was 32.
- Example 2 The absolute pressure of each decompression vent port when drying by the extruder 1 is as follows: absolute pressure of the first decompression vent port 360: 41.3 kPa, absolute pressure of the second decompression vent port 380: 41.3 kPa, third decompression vent.
- the absolute pressure of the port 390 was 36.3 kPa
- the absolute pressure of the fourth decompression vent port 400 was 31.3 kPa (the difference between the absolute pressure of the first decompression vent port 360 and the absolute pressure of the fourth decompression vent port 400).
- the operation of washing the acrylic rubber slurry and drying the acrylic rubber-containing crumb to continuously obtain solid acrylic rubber was continuously performed for 2 hours in the same manner as in Example 1. I went.
- Example 2 the water content of the water-containing crumb after passing through the dehydration zone 102 was 40% by weight. As a result, also in Example 2, vent-up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.2% by weight.
- the Mooney viscosity (ML1 + 4, 100 ° C.) of the obtained solid acrylic rubber was 34.
- Example 3 The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using the washing tank 7 and the extruder 1 shown in FIG. 1 to obtain a solid acrylic rubber.
- the supply rate of acrylic rubber to the cleaning tank 7 is 400 kg / h (supply rate in terms of solid rubber content), and the cleaning water is supplied to the cleaning tank 7. Washing was performed at a rate of 9600 kg / h.
- the acrylic rubber slurry after cleaning is passed through the water removal facility 8 (slit screen) from the cleaning tank 7 as a water content crumb (moisture content: 60% by weight) of the acrylic rubber (a mode in which water is accompanied by the water content crumb).
- the extruder 1 In the state where the water content is 60% by weight, the extruder 1 is supplied with a supply rate of 1000 kg / h (supply rate in terms of acrylic rubber (that is, the amount of acrylic rubber to be dried Q). ) was supplied at 400 kg / h) and dried by the extruder 1. Further, the temperature of the water-containing crumb of acrylic rubber at the time of charging into the extruder 1 was set to 40 ° C.
- the conditions for drying by the extruder 1 are the barrel temperature of the supply zone 100: 80 ° C., the barrel temperature of the dehydration zone 102: 130 ° C., and the barrel temperature of the drying zone 104: 160 ° C., and the absolute decompression vent port 360 Pressure: 41 kPa, absolute pressure of the second decompression vent port 380: 41 kPa, absolute pressure of the third decompression vent port 390: 30 kPa, and absolute pressure of the fourth decompression vent port 400: 25 kPa (absolute of the first decompression vent port 360).
- the water content of the water-containing crumb after passing through the dehydration zone 102 was 20% by weight.
- the washing tank 7 and the extruder 1 wash the acrylic rubber slurry and dry the water-containing crumb of the acrylic rubber to continuously obtain solid acrylic rubber for two hours continuously.
- venting up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.4% by weight.
- the Mooney viscosity (ML1 + 4, 100 ° C.) of the obtained solid acrylic rubber was 32.
- Example 4 The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using the washing tank 7 and the extruder 1 shown in FIG. 1 to obtain a solid acrylic rubber.
- the supply rate of acrylic rubber to the cleaning tank 7 when cleaning is performed in the cleaning tank 7 is 500 kg / h (supply rate in terms of solid rubber content), and the cleaning water is supplied to the cleaning tank 7. Washing was performed at a rate of 12000 kg / h.
- the acrylic rubber slurry after cleaning is passed through the water removal facility 8 (slit screen) from the cleaning tank 7 as a water content crumb (moisture content: 60% by weight) of the acrylic rubber (a mode in which water is accompanied by the water content crumb).
- the supply rate of 1250 kg / h to the extruder 1 (supply rate in terms of acrylic rubber (that is, the amount of acrylic rubber to be dried Q). ) was supplied at 500 kg / h) and dried by the extruder 1. Further, the temperature of the water-containing crumb of acrylic rubber at the time of charging into the extruder 1 was set to 65 ° C. The temperature of the water-containing crumb of acrylic rubber when it was put into the extruder 1 was adjusted by adjusting the temperature of the washing water when washing in the washing tank 7.
- the conditions for drying by the extruder 1 are the barrel temperature of the supply zone 100: 90 ° C., the barrel temperature of the dehydration zone 102: 140 ° C., and the barrel temperature of the drying zone 104: 170 ° C., and the absolute decompression vent port 360 Pressure: 65 kPa, absolute pressure of the second decompression vent port 380: 55 kPa, absolute pressure of the third decompression vent port 390: 40 kPa, and absolute pressure of the fourth decompression vent port 400: 35 kPa (absolute of the first decompression vent port 360).
- the water content of the water-containing crumb after passing through the dehydration zone 102 was 40% by weight.
- the washing tank 7 and the extruder 1 wash the acrylic rubber slurry and dry the water-containing crumb of the acrylic rubber to continuously obtain a solid acrylic rubber for 2 hours continuously.
- venting up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.4% by weight.
- the Mooney viscosity (ML1 + 4, 100 ° C.) of the obtained solid acrylic rubber was 32.
- each decompression vent port 360 when drying is performed by the extruder 1 The pressure of each decompression vent port 360 when drying is performed by the extruder 1, the absolute pressure of the first decompression vent port 360: 4 kPa, the absolute pressure of the second decompression vent port 380: 4 kPa, the absolute pressure of the third decompression vent port 390.
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Abstract
Provided is a method for producing an acrylic rubber, the method comprising a drying step for drying the acrylic rubber by using an extruder having a screw disposed inside a barrel in a rotationally drivable manner. An extruder having a plurality of reduced-pressure vent ports is used as the extruder, and the absolute pressure of a reduced-pressure vent port at an upstream side in the extrusion direction is set to be higher than the absolute pressure of a reduced-pressure vent port at a downstream side in the extrusion direction.
Description
本発明は、アクリルゴムの製造方法に関し、さらに詳しくは、ベントアップの発生を抑制しながら、アクリルゴムの含水率を適切に低減可能なアクリルゴムの製造方法に関する。
The present invention relates to a method for producing acrylic rubber, and more particularly to a method for producing acrylic rubber that can appropriately reduce the water content of acrylic rubber while suppressing the occurrence of vent-up.
アクリルゴムは、耐熱性、耐圧縮永久歪み性等の諸特性に優れるゴム架橋物が得られるゴム材料として、自動車用途を中心とした機能部品等に広く用いられている。また、アクリルゴムの製造過程では、ゴム重合体を塩析させた後に、押出機などにより押出乾燥する処理が行われる。
Acrylic rubber is widely used for functional parts mainly for automobile applications as a rubber material from which a crosslinked rubber product having excellent properties such as heat resistance and compression set resistance can be obtained. Further, in the process of producing acrylic rubber, a process of salting out the rubber polymer and then extruding and drying it with an extruder or the like is performed.
たとえば、特許文献1には、ゴム重合体を、押出機などにより押出乾燥する技術において、大気圧に連通し脱圧して気化物を大気に排出するベント口と、強制脱圧して気化物を排出する減圧ベント口とを備えた押出機を用いる技術が開示されている。この特許文献1においては、減圧ベント口を複数備えた押出機が例示されているが、複数の減圧ベント口の絶対圧力をいかなる条件とするかについては全く言及がなされていない。
For example, in Patent Document 1, in a technique of extruding and drying a rubber polymer by an extruder or the like, a vent port that communicates with atmospheric pressure to depressurize and discharge the vaporized material to the atmosphere and a vent port that forcibly depressurizes and discharges the vaporized material A technique for using an extruder equipped with a decompression vent port is disclosed. In Patent Document 1, an extruder having a plurality of decompression vent ports is exemplified, but no mention is made as to what condition the absolute pressure of the plurality of decompression vent ports should be.
また、特許文献2には、ゴム重合体を、押出機などにより押出乾燥する技術において、押出乾燥されたゴム重合体を、密閉されたスチーム流によりさらに乾燥させる技術が開示されている。この特許文献2においては、押出機先端からのゴム重合体の押出量や、押出機のスクリューの回転数、押出機先端内部におけるポリマーの圧力、さらには、押出機の比エネルギーなどの種々の条件を変更した際における、実験結果が開示されている。
Further, Patent Document 2 discloses a technique for extruding and drying a rubber polymer by an extruder or the like, in which the extruded rubber polymer is further dried by a sealed steam flow. In Patent Document 2, various conditions such as the amount of rubber polymer extruded from the tip of the extruder, the number of rotations of the screw of the extruder, the pressure of the polymer inside the tip of the extruder, and the specific energy of the extruder. The experimental results when the above is changed are disclosed.
さらに、特許文献3,4には、特許文献1や特許文献2のような押出機内においてゴム重合体の脱水、乾燥のみを行う技術とは異なり、押出機内において、ゴム重合体の塩析、ならびに、これに続いて、脱水および乾燥を行う技術が開示されている。これら特許文献3,4においては、押出機として、複数のベント口を有するものを用いる態様が例示されているが、特許文献3,4においても、複数のベント口の絶対圧力をいかなる条件とするかについては全く言及がなされていない。
Further, in Patent Documents 3 and 4, unlike the techniques of only dehydrating and drying the rubber polymer in the extruder as in Patent Document 1 and Patent Document 2, the salting of the rubber polymer and the salting of the rubber polymer in the extruder are provided. Following this, techniques for dehydration and drying are disclosed. In these Patent Documents 3 and 4, an embodiment in which an extruder having a plurality of vent ports is used as an extruder is exemplified, but also in Patent Documents 3 and 4, the absolute pressure of the plurality of vent ports is set as any condition. No mention is made of this.
押出機を用いた押出乾燥においては、アクリルゴムの脱水および乾燥を、この順で行うものであるが、アクリルゴムの乾燥効率を高め、これにより得られるアクリルゴムの含水率を低減するために、脱水に続く乾燥は、通常、減圧ベント口を介した減圧乾燥により行われる。しかしながら、減圧ベント口を介した減圧乾燥においては、減圧ベント口において、溶融したアクリルゴムが発泡し、アクリルゴムが減圧ベント口に流れ込むベントアップが発生してしまい、これにより生産性が低下してしまうという問題があった。
In extrusion drying using an extruder, the acrylic rubber is dehydrated and dried in this order. In order to increase the drying efficiency of the acrylic rubber and reduce the water content of the acrylic rubber obtained thereby, Drying following dehydration is usually performed by vacuum drying through a vacuum vent port. However, in decompression drying through the decompression vent port, molten acrylic rubber foams at the decompression vent port, causing vent-up in which the acrylic rubber flows into the decompression vent port, which reduces productivity. There was a problem that it would end up.
本発明は、このような実状に鑑みてなされたものであり、ベントアップの発生を抑制しながら、アクリルゴムの含水率を適切に低減可能なアクリルゴムの製造方法を提供することを目的とする。
The present invention has been made in view of such an actual situation, and an object of the present invention is to provide a method for producing acrylic rubber, which can appropriately reduce the water content of acrylic rubber while suppressing the occurrence of vent-up. ..
本発明者等は、上記目的を達成するために鋭意研究した結果、押出機を用いて、アクリルゴムの乾燥を行う際に、押出機として、減圧ベント口を複数有するものを用い、かつ、押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高くすることにより、上記目的を達成できることを見出し、本発明を完成させるに至った。
As a result of diligent research to achieve the above object, the present inventors have used an extruder having a plurality of pressure reducing vent ports when drying acrylic rubber, and extruded the acrylic rubber. We have found that the above object can be achieved by making the absolute pressure of the decompression vent port on the upstream side in the direction higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction, and have completed the present invention.
すなわち、本発明によれば、バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機として、減圧ベント口を複数有するものを用い、
押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高くする、アクリルゴムの製造方法が提供される。 That is, according to the present invention, it is a method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which screws are rotatably arranged inside a barrel.
As the extruder, one having a plurality of decompression vent ports was used.
Provided is a method for producing acrylic rubber in which the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is made higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
前記押出機として、減圧ベント口を複数有するものを用い、
押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高くする、アクリルゴムの製造方法が提供される。 That is, according to the present invention, it is a method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which screws are rotatably arranged inside a barrel.
As the extruder, one having a plurality of decompression vent ports was used.
Provided is a method for producing acrylic rubber in which the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is made higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
本発明において、押出方向上流側の減圧ベント口の絶対圧力と、押出方向下流側の減圧ベント口の絶対圧力との差を、5.0~94.0kPaの範囲とすることが好ましい。
本発明において、前記押出機として、前記減圧ベント口を2つ以上有するものを用い、2つ以上の前記減圧ベント口のうち、少なくとも2つの減圧ベント口の絶対圧力を、押出方向上流側から押出方向下流側に向かって、順に低くなるように設定することが好ましい。
本発明において、前記押出機として、複数の前記減圧ベント口に、覗き窓を有するものを用いることが好ましい。
本発明において、アクリルゴムを、含水クラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行うことが好ましい。
本発明において、アクリルゴムを、含水率60~70重量%であるクラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行うことが好ましい。 In the present invention, the difference between the absolute pressure of the decompression vent port on the upstream side in the extrusion direction and the absolute pressure of the decompression vent port on the downstream side in the extrusion direction is preferably in the range of 5.0 to 94.0 kPa.
In the present invention, the extruder having two or more decompression vent ports is used, and the absolute pressures of at least two decompression vent ports among the two or more decompression vent ports are extruded from the upstream side in the extrusion direction. It is preferable to set it so that it becomes lower in order toward the downstream side in the direction.
In the present invention, it is preferable to use an extruder having a plurality of viewing windows at the plurality of pressure reducing vent ports.
In the present invention, it is preferable that the acrylic rubber is put into the extruder in a hydrous crumb state to dry the acrylic rubber.
In the present invention, it is preferable that the acrylic rubber is put into the extruder in a crumb state having a water content of 60 to 70% by weight to dry the acrylic rubber.
本発明において、前記押出機として、前記減圧ベント口を2つ以上有するものを用い、2つ以上の前記減圧ベント口のうち、少なくとも2つの減圧ベント口の絶対圧力を、押出方向上流側から押出方向下流側に向かって、順に低くなるように設定することが好ましい。
本発明において、前記押出機として、複数の前記減圧ベント口に、覗き窓を有するものを用いることが好ましい。
本発明において、アクリルゴムを、含水クラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行うことが好ましい。
本発明において、アクリルゴムを、含水率60~70重量%であるクラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行うことが好ましい。 In the present invention, the difference between the absolute pressure of the decompression vent port on the upstream side in the extrusion direction and the absolute pressure of the decompression vent port on the downstream side in the extrusion direction is preferably in the range of 5.0 to 94.0 kPa.
In the present invention, the extruder having two or more decompression vent ports is used, and the absolute pressures of at least two decompression vent ports among the two or more decompression vent ports are extruded from the upstream side in the extrusion direction. It is preferable to set it so that it becomes lower in order toward the downstream side in the direction.
In the present invention, it is preferable to use an extruder having a plurality of viewing windows at the plurality of pressure reducing vent ports.
In the present invention, it is preferable that the acrylic rubber is put into the extruder in a hydrous crumb state to dry the acrylic rubber.
In the present invention, it is preferable that the acrylic rubber is put into the extruder in a crumb state having a water content of 60 to 70% by weight to dry the acrylic rubber.
本発明において、前記押出機として、複数の前記減圧ベント口よりも押出方向上流側に、押出方向上流側から順に、第1排出スリットおよび第2排出スリットを備えるものを用いることが好ましい。
In the present invention, it is preferable to use the extruder provided with a first discharge slit and a second discharge slit in order from the upstream side in the extrusion direction on the upstream side in the extrusion direction from the plurality of pressure reducing vent ports.
本発明において、前記押出機で単位時間当たりに乾燥されるアクリルゴムの処理量をQ[kg/h]、前記スクリューの回転数をN[rpm]としたとき、下記式(1)を満たすことが好ましい。
3≦Q/N≦8 (1)
本発明において、洗浄タンク内で、アクリルゴムを洗浄する洗浄工程をさらに備えるものとし、前記洗浄工程と前記乾燥工程とを、この順に連続工程とすることが好ましい。 In the present invention, when the processing amount of acrylic rubber dried by the extruder per unit time is Q [kg / h] and the rotation speed of the screw is N [rpm], the following formula (1) is satisfied. Is preferable.
3 ≦ Q / N ≦ 8 (1)
In the present invention, it is preferable that a cleaning step of cleaning the acrylic rubber is further provided in the cleaning tank, and the cleaning step and the drying step are continuous steps in this order.
3≦Q/N≦8 (1)
本発明において、洗浄タンク内で、アクリルゴムを洗浄する洗浄工程をさらに備えるものとし、前記洗浄工程と前記乾燥工程とを、この順に連続工程とすることが好ましい。 In the present invention, when the processing amount of acrylic rubber dried by the extruder per unit time is Q [kg / h] and the rotation speed of the screw is N [rpm], the following formula (1) is satisfied. Is preferable.
3 ≦ Q / N ≦ 8 (1)
In the present invention, it is preferable that a cleaning step of cleaning the acrylic rubber is further provided in the cleaning tank, and the cleaning step and the drying step are continuous steps in this order.
本発明によれば、ベントアップの発生を抑制しながら、アクリルゴムの含水率を適切に低減可能なアクリルゴムの製造方法の製造方法が提供される。
According to the present invention, there is provided a method for producing an acrylic rubber, which can appropriately reduce the water content of the acrylic rubber while suppressing the occurrence of vent-up.
本発明のアクリルゴムの製造方法は、バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機として、減圧ベント口を複数有するものを用い、
押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高く設定するものである。 The method for producing acrylic rubber of the present invention is a method for producing acrylic rubber, which comprises a drying step of drying the acrylic rubber using an extruder in which screws are rotatably arranged inside a barrel.
As the extruder, one having a plurality of decompression vent ports was used.
The absolute pressure of the decompression vent port on the upstream side in the extrusion direction is set higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
前記押出機として、減圧ベント口を複数有するものを用い、
押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高く設定するものである。 The method for producing acrylic rubber of the present invention is a method for producing acrylic rubber, which comprises a drying step of drying the acrylic rubber using an extruder in which screws are rotatably arranged inside a barrel.
As the extruder, one having a plurality of decompression vent ports was used.
The absolute pressure of the decompression vent port on the upstream side in the extrusion direction is set higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
<アクリルゴム>
まず、本発明の製造方法で用いるアクリルゴムについて説明する。
本発明の製造方法で用いるアクリルゴムは、分子中に、主成分(ゴム全単量体単位中、好ましくは30重量%以上有するものを言う。)としての(メタ)アクリル酸エステル単量体〔アクリル酸エステル単量体および/またはメタクリル酸エステル単量体の意。以下、(メタ)アクリル酸メチルなど同様。〕単位を含有するゴム状の重合体である。 <Acrylic rubber>
First, the acrylic rubber used in the production method of the present invention will be described.
The acrylic rubber used in the production method of the present invention has a (meth) acrylic acid ester monomer as a main component (preferably having 30% by weight or more in the total rubber monomer unit) in the molecule. Acrylic acid ester monomer and / or methacrylic acid ester monomer. Hereinafter, the same applies to methyl (meth) acrylate and the like. ] It is a rubber-like polymer containing a unit.
まず、本発明の製造方法で用いるアクリルゴムについて説明する。
本発明の製造方法で用いるアクリルゴムは、分子中に、主成分(ゴム全単量体単位中、好ましくは30重量%以上有するものを言う。)としての(メタ)アクリル酸エステル単量体〔アクリル酸エステル単量体および/またはメタクリル酸エステル単量体の意。以下、(メタ)アクリル酸メチルなど同様。〕単位を含有するゴム状の重合体である。 <Acrylic rubber>
First, the acrylic rubber used in the production method of the present invention will be described.
The acrylic rubber used in the production method of the present invention has a (meth) acrylic acid ester monomer as a main component (preferably having 30% by weight or more in the total rubber monomer unit) in the molecule. Acrylic acid ester monomer and / or methacrylic acid ester monomer. Hereinafter, the same applies to methyl (meth) acrylate and the like. ] It is a rubber-like polymer containing a unit.
本発明の製造方法で用いるアクリルゴムの主成分である(メタ)アクリル酸エステル単量体単位を形成する(メタ)アクリル酸エステル単量体としては、特に限定されないが、たとえば、(メタ)アクリル酸アルキルエステル単量体、および(メタ)アクリル酸アルコキシアルキルエステル単量体などを挙げることができる。
The (meth) acrylic acid ester monomer forming the (meth) acrylic acid ester monomer unit which is the main component of the acrylic rubber used in the production method of the present invention is not particularly limited, but for example, (meth) acrylic. Examples thereof include an acid alkyl ester monomer and a (meth) acrylic acid alkoxyalkyl ester monomer.
(メタ)アクリル酸アルキルエステル単量体としては、特に限定されないが、炭素数1~8のアルカノールと(メタ)アクリル酸とのエステルが好ましく、具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸2-エチルヘキシル、および(メタ)アクリル酸シクロヘキシルなどが挙げられる。これらの中でも、アルキル基の炭素数が2以上である、(メタ)アクリル酸アルキルエステル単量体が好ましく、(メタ)アクリル酸エチル、および(メタ)アクリル酸n-ブチルがより好ましく、アクリル酸エチル、およびアクリル酸n-ブチルが特に好ましい。これらは1種単独で、または2種以上を併せて使用することができる。
The (meth) acrylic acid alkyl ester monomer is not particularly limited, but an ester of alkanol having 1 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, methyl (meth) acrylic acid, ( Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) Examples thereof include 2-ethylhexyl acrylate and cyclohexyl (meth) acrylate. Among these, (meth) acrylic acid alkyl ester monomer having an alkyl group having 2 or more carbon atoms is preferable, ethyl (meth) acrylate and n-butyl (meth) acrylic acid are more preferable, and acrylic acid. Ethyl and n-butyl acrylate are particularly preferred. These can be used alone or in combination of two or more.
(メタ)アクリル酸アルコキシアルキルエステル単量体としては、特に限定されないが、炭素数2~8のアルコキシアルキルアルコールと(メタ)アクリル酸とのエステルが好ましく、具体的には、(メタ)アクリル酸メトキシメチル、(メタ)アクリル酸エトキシメチル、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸2-プロポキシエチル、(メタ)アクリル酸2-ブトキシエチル、(メタ)アクリル酸3-メトキシプロピル、および(メタ)アクリル酸4-メトキシブチルなどが挙げられる。これらの中でも、(メタ)アクリル酸2-エトキシエチル、および(メタ)アクリル酸2-メトキシエチルが好ましく、アクリル酸2-エトキシエチル、およびアクリル酸2-メトキシエチルが特に好ましい。これらは1種単独で、または2種以上を併せて使用することができる。
The (meth) acrylic acid alkoxyalkyl ester monomer is not particularly limited, but an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth) acrylic acid is preferable, and specifically, (meth) acrylic acid. Methoxymethyl, ethoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate , (Meta) acrylate 3-methoxypropyl, (meth) acrylate 4-methoxybutyl and the like. Among these, 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable, and 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly preferable. These can be used alone or in combination of two or more.
本発明の製造方法で用いるアクリルゴムにおいては、(メタ)アクリル酸エステル単量体単位として、(メタ)アクリル酸アルキルエステル単量体単位30~100重量%、および(メタ)アクリル酸アルコキシアルキルエステル単量体単位70~0重量%からなるものを用いることが好ましい。
In the acrylic rubber used in the production method of the present invention, the (meth) acrylic acid ester monomer unit includes 30 to 100% by weight of the (meth) acrylic acid alkyl ester monomer unit, and the (meth) acrylic acid alkoxyalkyl ester. It is preferable to use a monomer unit consisting of 70 to 0% by weight.
本発明の製造方法で用いるアクリルゴム中における、(メタ)アクリル酸エステル単量体単位の含有量は、好ましくは30重量%以上であり、より好ましくは50~99.9重量%、さらに好ましくは80~99.5重量%、特に好ましくは95~99.5重量%である。(メタ)アクリル酸エステル単量体単位の含有量が少なすぎると、得られるゴム架橋物の耐候性、耐熱性、および耐油性が低下するおそれがあり、一方、多すぎると、得られるゴム架橋物の機械的強度が低下するおそれがある。
The content of the (meth) acrylic acid ester monomer unit in the acrylic rubber used in the production method of the present invention is preferably 30% by weight or more, more preferably 50 to 99.9% by weight, still more preferably. It is 80 to 99.5% by weight, particularly preferably 95 to 99.5% by weight. If the content of the (meth) acrylic acid ester monomer unit is too small, the weather resistance, heat resistance, and oil resistance of the obtained rubber crosslinked product may decrease, while if it is too large, the obtained rubber crosslinked product may be deteriorated. The mechanical strength of the object may decrease.
本発明の製造方法で用いるアクリルゴムは、(メタ)アクリル酸アルキルエステル単量体単位に加えて、必要に応じて、架橋性単量体単位を含有していてもよい。架橋性単量体単位を形成する架橋性単量体としては、特に限定されないが、たとえば、α,β-エチレン性不飽和カルボン酸単量体;エポキシ基を有する単量体;ハロゲン原子を有する単量体;ジエン単量体;などが挙げられる。
The acrylic rubber used in the production method of the present invention may contain a crosslinkable monomer unit in addition to the (meth) acrylic acid alkyl ester monomer unit, if necessary. The crosslinkable monomer forming the crosslinkable monomer unit is not particularly limited, and is, for example, an α, β-ethylene unsaturated carboxylic acid monomer; a monomer having an epoxy group; having a halogen atom. Monomer; diene monomer; and the like.
α,β-エチレン性不飽和カルボン酸単量体単位を形成するα,β-エチレン性不飽和カルボン酸単量体としては、特に限定されないが、たとえば、炭素数3~12のα,β-エチレン性不飽和モノカルボン酸、炭素数4~12のα,β-エチレン性不飽和ジカルボン酸、および炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルなどが挙げられる。α,β-エチレン性不飽和カルボン酸単量体を用いることにより、アクリルゴムを、カルボキシル基を架橋点として持つカルボキシル基含有アクリルゴムとすることができ、これにより、ゴム架橋物とした場合における、耐圧縮永久歪み性をより高めることができる。
The α, β-ethylenically unsaturated carboxylic acid monomer forming the α, β-ethylenically unsaturated carboxylic acid monomer unit is not particularly limited, and is, for example, α, β- having 3 to 12 carbon atoms. Ethylene unsaturated monocarboxylic acid, α, β-ethylene unsaturated dicarboxylic acid with 4 to 12 carbon atoms, α, β-ethylenically unsaturated dicarboxylic acid with 4 to 12 carbon atoms and alkanol with 1 to 8 carbon atoms And monoester with. By using the α, β-ethylenically unsaturated carboxylic acid monomer, the acrylic rubber can be made into a carboxyl group-containing acrylic rubber having a carboxyl group as a cross-linking point, whereby a rubber cross-linked product can be obtained. , The compression resistance and permanent strain resistance can be further improved.
炭素数3~12のα,β-エチレン性不飽和モノカルボン酸の具体例としては、アクリル酸、メタクリル酸、α-エチルアクリル酸、クロトン酸、およびケイ皮酸などが挙げられる。
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸の具体例としては、フマル酸、マレイン酸などのブテンジオン酸;イタコン酸;シトラコン酸;クロロマレイン酸;などが挙げられる。
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルの具体例としては、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノn-ブチル、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノn-ブチルなどのブテンジオン酸モノ鎖状アルキルエステル;フマル酸モノシクロペンチル、フマル酸モノシクロヘキシル、フマル酸モノシクロヘキセニル、マレイン酸モノシクロペンチル、マレイン酸モノシクロヘキシル、マレイン酸モノシクロヘキセニルなどの脂環構造を有するブテンジオン酸モノエステル;イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノn-ブチル、イタコン酸モノシクロヘキシルなどのイタコン酸モノエステル;などが挙げられる。
これらの中でも、炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルが好ましく、ブテンジオン酸モノ鎖状アルキルエステル、または脂環構造を有するブテンジオン酸モノエステルがより好ましく、フマル酸モノn-ブチル、マレイン酸モノn-ブチル、フマル酸モノシクロヘキシル、およびマレイン酸モノシクロヘキシルがさらに好ましく、フマル酸モノn-ブチルが特に好ましい。これらのα,β-エチレン性不飽和カルボン酸単量体は、1種単独で、または2種以上を併せて使用することができる。なお、上記単量体のうち、ジカルボン酸には、無水物として存在しているものも含まれる。 Specific examples of the α, β-ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and cinnamic acid.
Specific examples of the α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butendioic acids such as fumaric acid and maleic acid; itaconic acid; citraconic acid; chloromaleic acid; and the like.
Specific examples of the monoester of α, β-ethylenic unsaturated dicarboxylic acid having 4 to 12 carbon atoms and alkanol having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, and malein. Itaconic acid monochain alkyl esters such as monomethyl acid, monoethyl maleate, monon-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, maleine Examples thereof include butenedioic acid monoesters having an alicyclic structure such as monocyclohexenyl acid acid; itaconic acid monoesters such as monomethyl itaconic acid, monoethyl itaconic acid, monon-butyl itaconic acid, and monocyclohexyl itaconic acid.
Among these, a monoester of α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkanol having 1 to 8 carbon atoms is preferable, and a monoester of butendioic acid or butendion having an alicyclic structure Acid monoesters are more preferred, mono-n-butyl fumarate, mono n-butyl maleate, monocyclohexyl fumarate, and monocyclohexyl maleate are even more preferred, and mono n-butyl fumarate is particularly preferred. These α, β-ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more. Of the above-mentioned monomers, the dicarboxylic acid also includes those existing as anhydrides.
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸の具体例としては、フマル酸、マレイン酸などのブテンジオン酸;イタコン酸;シトラコン酸;クロロマレイン酸;などが挙げられる。
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルの具体例としては、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノn-ブチル、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノn-ブチルなどのブテンジオン酸モノ鎖状アルキルエステル;フマル酸モノシクロペンチル、フマル酸モノシクロヘキシル、フマル酸モノシクロヘキセニル、マレイン酸モノシクロペンチル、マレイン酸モノシクロヘキシル、マレイン酸モノシクロヘキセニルなどの脂環構造を有するブテンジオン酸モノエステル;イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノn-ブチル、イタコン酸モノシクロヘキシルなどのイタコン酸モノエステル;などが挙げられる。
これらの中でも、炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルが好ましく、ブテンジオン酸モノ鎖状アルキルエステル、または脂環構造を有するブテンジオン酸モノエステルがより好ましく、フマル酸モノn-ブチル、マレイン酸モノn-ブチル、フマル酸モノシクロヘキシル、およびマレイン酸モノシクロヘキシルがさらに好ましく、フマル酸モノn-ブチルが特に好ましい。これらのα,β-エチレン性不飽和カルボン酸単量体は、1種単独で、または2種以上を併せて使用することができる。なお、上記単量体のうち、ジカルボン酸には、無水物として存在しているものも含まれる。 Specific examples of the α, β-ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and cinnamic acid.
Specific examples of the α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butendioic acids such as fumaric acid and maleic acid; itaconic acid; citraconic acid; chloromaleic acid; and the like.
Specific examples of the monoester of α, β-ethylenic unsaturated dicarboxylic acid having 4 to 12 carbon atoms and alkanol having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, and malein. Itaconic acid monochain alkyl esters such as monomethyl acid, monoethyl maleate, monon-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, maleine Examples thereof include butenedioic acid monoesters having an alicyclic structure such as monocyclohexenyl acid acid; itaconic acid monoesters such as monomethyl itaconic acid, monoethyl itaconic acid, monon-butyl itaconic acid, and monocyclohexyl itaconic acid.
Among these, a monoester of α, β-ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkanol having 1 to 8 carbon atoms is preferable, and a monoester of butendioic acid or butendion having an alicyclic structure Acid monoesters are more preferred, mono-n-butyl fumarate, mono n-butyl maleate, monocyclohexyl fumarate, and monocyclohexyl maleate are even more preferred, and mono n-butyl fumarate is particularly preferred. These α, β-ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more. Of the above-mentioned monomers, the dicarboxylic acid also includes those existing as anhydrides.
エポキシ基を有する単量体としては、特に限定されないが、たとえば、(メタ)アクリル酸グリシジルなどのエポキシ基含有(メタ)アクリル酸エステル;アリルグリシジルエーテルおよびビニルグリシジルエーテルなどのエポキシ基含有エーテル;などが挙げられる。
The monomer having an epoxy group is not particularly limited, and for example, an epoxy group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate; an epoxy group-containing ether such as allyl glycidyl ether and vinyl glycidyl ether; Can be mentioned.
ハロゲン原子を有する単量体としては、特に限定されないが、たとえば、ハロゲン含有飽和カルボン酸の不飽和アルコールエステル、(メタ)アクリル酸ハロアルキルエステル、(メタ)アクリル酸ハロアシロキシアルキルエステル、(メタ)アクリル酸(ハロアセチルカルバモイルオキシ)アルキルエステル、ハロゲン含有不飽和エーテル、ハロゲン含有不飽和ケトン、ハロメチル基含有芳香族ビニル化合物、ハロゲン含有不飽和アミド、およびハロアセチル基含有不飽和単量体などが挙げられる。
The monomer having a halogen atom is not particularly limited, and for example, an unsaturated alcohol ester of a halogen-containing saturated carboxylic acid, a (meth) acrylic acid haloalkyl ester, a (meth) acrylic acid haloacyloxyalkyl ester, or (meth) acrylic. Examples thereof include acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers.
ハロゲン含有飽和カルボン酸の不飽和アルコールエステルの具体例としては、クロロ酢酸ビニル、2-クロロプロピオン酸ビニル、およびクロロ酢酸アリルなどが挙げられる。
(メタ)アクリル酸ハロアルキルエステルの具体例としては、(メタ)アクリル酸クロロメチル、(メタ)アクリル酸1-クロロエチル、(メタ)アクリル酸2-クロロエチル、(メタ)アクリル酸1,2-ジクロロエチル、(メタ)アクリル酸2-クロロプロピル、(メタ)アクリル酸3-クロロプロピル、および(メタ)アクリル酸2,3-ジクロロプロピルなどが挙げられる。
(メタ)アクリル酸ハロアシロキシアルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセトキシ)エチル、(メタ)アクリル酸2-(クロロアセトキシ)プロピル、(メタ)アクリル酸3-(クロロアセトキシ)プロピル、および(メタ)アクリル酸3-(ヒドロキシクロロアセトキシ)プロピルなどが挙げられる。
(メタ)アクリル酸(ハロアセチルカルバモイルオキシ)アルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセチルカルバモイルオキシ)エチル、および(メタ)アクリル酸3-(クロロアセチルカルバモイルオキシ)プロピルなどが挙げられる。 Specific examples of unsaturated alcohol esters of halogen-containing saturated carboxylic acids include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
Specific examples of the (meth) acrylic acid haloalkyl ester include chloromethyl (meth) acrylic acid, 1-chloroethyl (meth) acrylic acid, 2-chloroethyl (meth) acrylic acid, and 1,2-dichloroethyl (meth) acrylic acid. , 2-Chloropropyl (meth) acrylic acid, 3-chloropropyl (meth) acrylic acid, and 2,3-dichloropropyl (meth) acrylic acid.
Specific examples of the (meth) acrylic acid haloacyloxyalkyl ester include (meth) acrylic acid 2- (chloroacetoxy) ethyl, (meth) acrylic acid 2- (chloroacetoxy) propyl, and (meth) acrylic acid 3- (chloro). Examples thereof include acetoxy) propyl and 3- (hydroxychloroacetoxy) propyl (meth) acrylate.
Specific examples of the (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl ester include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylic acid and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylic acid. Can be mentioned.
(メタ)アクリル酸ハロアルキルエステルの具体例としては、(メタ)アクリル酸クロロメチル、(メタ)アクリル酸1-クロロエチル、(メタ)アクリル酸2-クロロエチル、(メタ)アクリル酸1,2-ジクロロエチル、(メタ)アクリル酸2-クロロプロピル、(メタ)アクリル酸3-クロロプロピル、および(メタ)アクリル酸2,3-ジクロロプロピルなどが挙げられる。
(メタ)アクリル酸ハロアシロキシアルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセトキシ)エチル、(メタ)アクリル酸2-(クロロアセトキシ)プロピル、(メタ)アクリル酸3-(クロロアセトキシ)プロピル、および(メタ)アクリル酸3-(ヒドロキシクロロアセトキシ)プロピルなどが挙げられる。
(メタ)アクリル酸(ハロアセチルカルバモイルオキシ)アルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセチルカルバモイルオキシ)エチル、および(メタ)アクリル酸3-(クロロアセチルカルバモイルオキシ)プロピルなどが挙げられる。 Specific examples of unsaturated alcohol esters of halogen-containing saturated carboxylic acids include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
Specific examples of the (meth) acrylic acid haloalkyl ester include chloromethyl (meth) acrylic acid, 1-chloroethyl (meth) acrylic acid, 2-chloroethyl (meth) acrylic acid, and 1,2-dichloroethyl (meth) acrylic acid. , 2-Chloropropyl (meth) acrylic acid, 3-chloropropyl (meth) acrylic acid, and 2,3-dichloropropyl (meth) acrylic acid.
Specific examples of the (meth) acrylic acid haloacyloxyalkyl ester include (meth) acrylic acid 2- (chloroacetoxy) ethyl, (meth) acrylic acid 2- (chloroacetoxy) propyl, and (meth) acrylic acid 3- (chloro). Examples thereof include acetoxy) propyl and 3- (hydroxychloroacetoxy) propyl (meth) acrylate.
Specific examples of the (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl ester include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylic acid and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylic acid. Can be mentioned.
ハロゲン含有不飽和エーテルの具体例としては、クロロメチルビニルエーテル、2-クロロエチルビニルエーテル、3-クロロプロピルビニルエーテル、2-クロロエチルアリルエーテル、および3-クロロプロピルアリルエーテルなどが挙げられる。
ハロゲン含有不飽和ケトンの具体例としては、2-クロロエチルビニルケトン、3-クロロプロピルビニルケトン、および2-クロロエチルアリルケトンなどが挙げられる。
ハロメチル基含有芳香族ビニル化合物の具体例としては、p-クロロメチルスチレン、m-クロロメチルスチレン、o-クロロメチルスチレン、およびp-クロロメチル-α-メチルスチレンなどが挙げられる。 Specific examples of the halogen-containing unsaturated ether include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether and the like.
Specific examples of the halogen-containing unsaturated ketone include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone and the like.
Specific examples of the halomethyl group-containing aromatic vinyl compound include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl-α-methylstyrene.
ハロゲン含有不飽和ケトンの具体例としては、2-クロロエチルビニルケトン、3-クロロプロピルビニルケトン、および2-クロロエチルアリルケトンなどが挙げられる。
ハロメチル基含有芳香族ビニル化合物の具体例としては、p-クロロメチルスチレン、m-クロロメチルスチレン、o-クロロメチルスチレン、およびp-クロロメチル-α-メチルスチレンなどが挙げられる。 Specific examples of the halogen-containing unsaturated ether include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether and the like.
Specific examples of the halogen-containing unsaturated ketone include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone and the like.
Specific examples of the halomethyl group-containing aromatic vinyl compound include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl-α-methylstyrene.
ハロゲン含有不飽和アミドの具体例としては、N-クロロメチル(メタ)アクリルアミドなどが挙げられる。
ハロアセチル基含有不飽和単量体の具体例としては、3-(ヒドロキシクロロアセトキシ)プロピルアリルエーテル、p-ビニルベンジルクロロ酢酸エステルなどが挙げられる。 Specific examples of the halogen-containing unsaturated amide include N-chloromethyl (meth) acrylamide.
Specific examples of the haloacetyl group-containing unsaturated monomer include 3- (hydroxychloroacetoxy) propylallyl ether and p-vinylbenzylchloroacetic acid ester.
ハロアセチル基含有不飽和単量体の具体例としては、3-(ヒドロキシクロロアセトキシ)プロピルアリルエーテル、p-ビニルベンジルクロロ酢酸エステルなどが挙げられる。 Specific examples of the halogen-containing unsaturated amide include N-chloromethyl (meth) acrylamide.
Specific examples of the haloacetyl group-containing unsaturated monomer include 3- (hydroxychloroacetoxy) propylallyl ether and p-vinylbenzylchloroacetic acid ester.
ジエン単量体としては、共役ジエン単量体、非共役ジエン単量体が挙げられる。
共役ジエン単量体の具体例としては、1,3-ブタジエン、イソプレン、およびピペリレンなどを挙げることができる。
非共役ジエン単量体の具体例としては、エチリデンノルボルネン、ジシクロペンタジエン、(メタ)アクリル酸ジシクロペンタジエニル、および(メタ)アクリル酸2-ジシクロペンタジエニルエチルなどを挙げることができる。 Examples of the diene monomer include a conjugated diene monomer and a non-conjugated diene monomer.
Specific examples of the conjugated diene monomer include 1,3-butadiene, isoprene, and piperylene.
Specific examples of the non-conjugated diene monomer include ethylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate. ..
共役ジエン単量体の具体例としては、1,3-ブタジエン、イソプレン、およびピペリレンなどを挙げることができる。
非共役ジエン単量体の具体例としては、エチリデンノルボルネン、ジシクロペンタジエン、(メタ)アクリル酸ジシクロペンタジエニル、および(メタ)アクリル酸2-ジシクロペンタジエニルエチルなどを挙げることができる。 Examples of the diene monomer include a conjugated diene monomer and a non-conjugated diene monomer.
Specific examples of the conjugated diene monomer include 1,3-butadiene, isoprene, and piperylene.
Specific examples of the non-conjugated diene monomer include ethylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate. ..
上記架橋性単量体の中でも、α,β-エチレン性不飽和カルボン酸単量体を用いた場合には、アクリルゴムをカルボキシル基含有アクリルゴムとすることができる。アクリルゴムを、カルボキシル基含有アクリルゴムとすることにより、耐油性、耐熱性を良好なものとしながら、耐圧縮永久歪み性を向上させることができる。
Among the above crosslinkable monomers, when an α, β-ethylenically unsaturated carboxylic acid monomer is used, the acrylic rubber can be a carboxyl group-containing acrylic rubber. By using a carboxyl group-containing acrylic rubber as the acrylic rubber, it is possible to improve the compression resistance and permanent strain resistance while improving the oil resistance and heat resistance.
本発明の製造方法で用いるアクリルゴム中における、架橋性単量体単位の含有量は、好ましくは0.01重量%以上であり、より好ましくは0.1~50重量%、さらに好ましくは0.5~20重量%、特に好ましくは0.5~5重量%である。架橋性単量体単位の含有量を上記範囲とすることにより、得られるゴム架橋物の機械的特性や耐熱性を良好なものとしながら、耐圧縮永久歪み性をより適切に高めることができる。
The content of the crosslinkable monomer unit in the acrylic rubber used in the production method of the present invention is preferably 0.01% by weight or more, more preferably 0.1 to 50% by weight, still more preferably 0. It is 5 to 20% by weight, particularly preferably 0.5 to 5% by weight. By setting the content of the crosslinkable monomer unit in the above range, it is possible to more appropriately enhance the compression resistance to permanent strain while improving the mechanical properties and heat resistance of the obtained rubber crosslinked product.
本発明の製造方法で用いるアクリルゴムは、(メタ)アクリル酸エステル単量体単位、および必要に応じて用いられる架橋性単量体単位に加えて、これらと共重合可能な他の単量体の単位を有していてもよい。このような共重合可能な他の単量体としては、芳香族ビニル単量体、α,β-エチレン性不飽和ニトリル単量体、アクリルアミド系単量体、α,β-エチレン性不飽和ジカルボン酸ジエステル単量体、その他のオレフィン系単量体などが挙げられる。
The acrylic rubber used in the production method of the present invention is, in addition to the (meth) acrylic acid ester monomer unit and the crosslinkable monomer unit used as needed, other monomers copolymerizable with these. It may have a unit of. Other such copolymerizable monomers include aromatic vinyl monomers, α, β-ethylenic unsaturated nitrile monomers, acrylamide-based monomers, and α, β-ethylenic unsaturated dicarboxylics. Examples thereof include acid diester monomers and other olefin-based monomers.
芳香族ビニル単量体としては、スチレン、α-メチルスチレン、ジビニルベンゼンなどが挙げられる。
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and divinylbenzene.
α,β-エチレン性不飽和ニトリル単量体としては、アクリロニトリル、メタクリロニトリルなどが挙げられる。
アクリルアミド系単量体としては、アクリルアミド、メタクリルアミドなどが挙げられる。
α,β-エチレン性不飽和ジカルボン酸ジエステル単量体としては、マレイン酸ジメチル、マレイン酸ジn-ブチルなどのマレイン酸ジアルキルエステルであってアルキル基の炭素数が1~18のもの;フマル酸ジメチル、フマル酸ジn-ブチルなどのフマル酸ジアルキルエステルであってアルキル基の炭素数が1~18のもの;マレイン酸ジシクロペンチル、マレイン酸ジシクロヘキシルなどのマレイン酸ジシクロアルキルエステルであってシクロアルキル基の炭素数が4~16のもの;フマル酸ジシクロペンチル、フマル酸ジシクロヘキシルなどのフマル酸ジシクロアルキルエステルであってシクロアルキル基の炭素数が4~16のもの;イタコン酸ジメチル、イタコン酸ジn-ブチルなどのイタコン酸ジアルキルエステルであってアルキル基の炭素数が1~18のもの:イタコン酸ジシクロヘキシルなどのイタコン酸ジシクロアルキルエステルであってシクロアルキル基の炭素数が4~16のもの;などが挙げられる。
その他のオレフィン系単量体としては、エチレン、プロピレン、塩化ビニル、塩化ビニリデン、酢酸ビニル、エチルビニルエーテル、ブチルビニルエーテルなどが挙げられる。 Examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
Examples of the acrylamide-based monomer include acrylamide and methacrylamide.
The α, β-ethylenic unsaturated dicarboxylic acid diester monomer is a maleic acid dialkyl ester such as dimethyl maleate or din-butyl maleate having an alkyl group having 1 to 18 carbon atoms; fumaric acid. A fumaric acid dialkyl ester such as dimethyl or din-butyl fumarate having an alkyl group having 1 to 18 carbon atoms; a dicyclopentyl maleate such as dicyclopentyl maleate or dicyclohexyl maleate and a cycloalkyl ester. A group having 4 to 16 carbon atoms; a dicycloalkyl ester of fumaric acid such as dicyclopentyl fumarate and dicyclohexyl fumarate having a cycloalkyl group having 4 to 16 carbon atoms; dimethyl itaconate, di-itaconate Itaconic acid dialkyl ester such as n-butyl having an alkyl group having 1 to 18 carbon atoms: an itaconic acid dicycloalkyl ester such as dicyclohexyl itaconate having a cycloalkyl group having 4 to 16 carbon atoms. ; And so on.
Examples of other olefin-based monomers include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, ethyl vinyl ether, and butyl vinyl ether.
アクリルアミド系単量体としては、アクリルアミド、メタクリルアミドなどが挙げられる。
α,β-エチレン性不飽和ジカルボン酸ジエステル単量体としては、マレイン酸ジメチル、マレイン酸ジn-ブチルなどのマレイン酸ジアルキルエステルであってアルキル基の炭素数が1~18のもの;フマル酸ジメチル、フマル酸ジn-ブチルなどのフマル酸ジアルキルエステルであってアルキル基の炭素数が1~18のもの;マレイン酸ジシクロペンチル、マレイン酸ジシクロヘキシルなどのマレイン酸ジシクロアルキルエステルであってシクロアルキル基の炭素数が4~16のもの;フマル酸ジシクロペンチル、フマル酸ジシクロヘキシルなどのフマル酸ジシクロアルキルエステルであってシクロアルキル基の炭素数が4~16のもの;イタコン酸ジメチル、イタコン酸ジn-ブチルなどのイタコン酸ジアルキルエステルであってアルキル基の炭素数が1~18のもの:イタコン酸ジシクロヘキシルなどのイタコン酸ジシクロアルキルエステルであってシクロアルキル基の炭素数が4~16のもの;などが挙げられる。
その他のオレフィン系単量体としては、エチレン、プロピレン、塩化ビニル、塩化ビニリデン、酢酸ビニル、エチルビニルエーテル、ブチルビニルエーテルなどが挙げられる。 Examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
Examples of the acrylamide-based monomer include acrylamide and methacrylamide.
The α, β-ethylenic unsaturated dicarboxylic acid diester monomer is a maleic acid dialkyl ester such as dimethyl maleate or din-butyl maleate having an alkyl group having 1 to 18 carbon atoms; fumaric acid. A fumaric acid dialkyl ester such as dimethyl or din-butyl fumarate having an alkyl group having 1 to 18 carbon atoms; a dicyclopentyl maleate such as dicyclopentyl maleate or dicyclohexyl maleate and a cycloalkyl ester. A group having 4 to 16 carbon atoms; a dicycloalkyl ester of fumaric acid such as dicyclopentyl fumarate and dicyclohexyl fumarate having a cycloalkyl group having 4 to 16 carbon atoms; dimethyl itaconate, di-itaconate Itaconic acid dialkyl ester such as n-butyl having an alkyl group having 1 to 18 carbon atoms: an itaconic acid dicycloalkyl ester such as dicyclohexyl itaconate having a cycloalkyl group having 4 to 16 carbon atoms. ; And so on.
Examples of other olefin-based monomers include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, ethyl vinyl ether, and butyl vinyl ether.
これら共重合可能な他の単量体の中でも、スチレン、アクリロニトリル、メタクリロニトリル、エチレンおよび酢酸ビニルが好ましく、アクリロニトリル、メタクリロニトリル、およびエチレンがより好ましい。
Among these other copolymerizable monomers, styrene, acrylonitrile, methacrylonitrile, ethylene and vinyl acetate are preferable, and acrylonitrile, methacrylonitrile, and ethylene are more preferable.
共重合可能な他の単量体は、1種単独で、または2種以上を併せて使用することができる。本発明のアクリルゴム中における、これら共重合可能な他の単量体の単位の含有量は、通常、49.9重量%以下、好ましくは19.5重量%以下、より好ましくは10重量%以下、さらに好ましくは4.5重量%以下である。
Other copolymerizable monomers can be used alone or in combination of two or more. The content of the unit of these other copolymerizable monomers in the acrylic rubber of the present invention is usually 49.9% by weight or less, preferably 19.5% by weight or less, and more preferably 10% by weight or less. , More preferably 4.5% by weight or less.
なお、本発明の製造方法で用いるアクリルゴムを、共重合可能な他の単量体の単位を含有するものとする場合には、その含有量は、上記範囲とすればよいが、なかでも、エチレン単位を有するものとする場合には、エチレン単位の含有量は、10重量%以下とすることが好ましく、4.5重量%以下とすることがさらに好ましい。同様に、本発明の製造方法で用いるアクリルゴムを、アクリロニトリル単位や、メタクリロニトリル単位を有するものとする場合にも、アクリロニトリル単位およびメタクリロニトリル単位の合計の含有量を、10重量%以下とすることが好ましく、4.5重量%以下とすることがさらに好ましい。
When the acrylic rubber used in the production method of the present invention contains a unit of another copolymerizable monomer, the content may be in the above range. When it has ethylene units, the content of ethylene units is preferably 10% by weight or less, and more preferably 4.5% by weight or less. Similarly, when the acrylic rubber used in the production method of the present invention has an acrylonitrile unit or a methacrylonitrile unit, the total content of the acrylonitrile unit and the methacrylonitrile unit shall be 10% by weight or less. It is preferable to use 4.5% by weight or less.
本発明の製造方法で用いるアクリルゴムは、上記各単量体を重合することにより得ることが好ましい。重合反応の形態としては、乳化重合法、懸濁重合法、塊状重合法、および溶液重合法のいずれも用いることができるが、重合反応の制御の容易性などの点から、公知のアクリルゴムの製造法として一般的に用いられている常圧下での乳化重合法や溶液重合法によるのが好ましく、乳化重合法によれば、アクリルゴムを、ラテックスの形態(アクリルゴムのラテックス)にて得ることができ、溶液重合法によれば、アクリルゴムを、重合体溶液の形態(アクリルゴムの重合体溶液)にて得ることができる。重合は、回分式、半回分式、連続式のいずれでもよい。重合は、通常、0~70℃、好ましくは5~50℃の温度範囲で行われる。
The acrylic rubber used in the production method of the present invention is preferably obtained by polymerizing each of the above monomers. As the form of the polymerization reaction, any of an emulsion polymerization method, a suspension polymerization method, a massive polymerization method, and a solution polymerization method can be used, but from the viewpoint of ease of control of the polymerization reaction, known acrylic rubber It is preferable to use an emulsion polymerization method or a solution polymerization method under normal pressure, which is generally used as a production method. According to the emulsion polymerization method, acrylic rubber is obtained in the form of latex (latex of acrylic rubber). According to the solution polymerization method, acrylic rubber can be obtained in the form of a polymer solution (polymer solution of acrylic rubber). The polymerization may be a batch type, a semi-batch type, or a continuous type. The polymerization is usually carried out in a temperature range of 0 to 70 ° C, preferably 5 to 50 ° C.
そして、得られたアクリルゴムのラテックスについては、凝固剤を用いて凝固させる方法により、アクリルゴムの重合体溶液については、水および必要に応じて凝固剤を添加した水を用いて凝固させる方法により、アクリルゴムの含水クラム、具体的には、アクリルゴムのクラムとセラム水の混合物(以下、「クラムスラリー」とする)を得ることができる。ここで、セラム水とは、凝固剤や重合副資材残渣などが含まれていてもよい(凝固剤や重合副資材残渣などが、溶解または分散していてもよい)水のことを意味し、本実施形態では、アクリルゴムのクラムと同伴される水、あるいは、アクリルゴムのクラムと同伴され、後に分離される水のいずれをも、セラム水とする。また、本実施形態では、洗浄や乾燥などにより、溶解または分散している成分の種類や量が変化した場合をも含めて、セラム水とする。凝固剤の具体例としては、塩化カルシウム、塩化マグネシウム、塩化ナトリウム、硫酸マグネシウム、塩化バリウムなどが挙げられる。
Then, the obtained acrylic rubber latex is coagulated with a coagulant, and the acrylic rubber polymer solution is coagulated with water and, if necessary, water with a coagulant added. , Acrylic rubber hydrous crumb, specifically, a mixture of acrylic rubber crumb and serum water (hereinafter referred to as "clam slurry") can be obtained. Here, the serum water means water that may contain a coagulant, a polymerization auxiliary material residue, or the like (a coagulant, a polymerization auxiliary material residue, or the like may be dissolved or dispersed). In the present embodiment, either the water associated with the acrylic rubber crumb or the water accompanying the acrylic rubber crumb and later separated is defined as serum water. Further, in the present embodiment, the serum water is used including the case where the type and amount of the dissolved or dispersed components are changed due to washing or drying. Specific examples of the coagulant include calcium chloride, magnesium chloride, sodium chloride, magnesium sulfate, barium chloride and the like.
<アクリルゴムの製造方法>
次いで、本発明のアクリルゴムの製造方法について、説明する。
図1は、本発明の実施形態に係るアクリルゴムの製造方法に用いる洗浄タンクおよび押出機を示す概略図である。 <Acrylic rubber manufacturing method>
Next, the method for producing the acrylic rubber of the present invention will be described.
FIG. 1 is a schematic view showing a cleaning tank and an extruder used in the method for producing acrylic rubber according to the embodiment of the present invention.
次いで、本発明のアクリルゴムの製造方法について、説明する。
図1は、本発明の実施形態に係るアクリルゴムの製造方法に用いる洗浄タンクおよび押出機を示す概略図である。 <Acrylic rubber manufacturing method>
Next, the method for producing the acrylic rubber of the present invention will be described.
FIG. 1 is a schematic view showing a cleaning tank and an extruder used in the method for producing acrylic rubber according to the embodiment of the present invention.
以下においては、本発明のアクリルゴムの製造方法に用いる製造装置として、図1に示す一実施形態に係る洗浄タンクおよび押出機を使用する場合を例示して、上記のように乳化重合または溶液重合を行った後、凝固することにより得られるクラムスラリー(より具体的には、クラムスラリー中に含まれる含水クラム)について、洗浄を行い、次いで、乾燥を行うことで、固形状のアクリルゴムを得る方法について説明する。
In the following, the case where the washing tank and the extruder according to the embodiment shown in FIG. 1 are used as the manufacturing apparatus used in the method for manufacturing the acrylic rubber of the present invention will be illustrated, and emulsion polymerization or solution polymerization will be carried out as described above. The crumb slurry (more specifically, the water-containing crumb contained in the crumb slurry) obtained by solidification is washed and then dried to obtain a solid acrylic rubber. The method will be described.
図1に示すように、本実施形態に係る製造装置は、押出機1と、洗浄タンク7を備える。上記した方法にしたがって得られるクラムスラリーは、図1に示すように、洗浄タンク7に連続的に供給され、洗浄タンク7内で、クラムスラリー中に含まれる含水クラムの洗浄が行われる。洗浄タンク7においては、洗浄されたクラムスラリー(より具体的には、洗浄された含水クラムを含むクラムスラリー)が、洗浄タンク7から連続的に排出され、連続的に排出されたクラムスラリー(より具体的には、洗浄された含水クラムを含むクラムスラリー)は、洗浄タンク7に設けられた排出口から、押出機1のフィード口310に連続的に供給されるようになっている。より具体的には、洗浄されたクラムスラリーは、洗浄タンク7に設けられた排出口から連続的に排出され、図1に示す水除去設備8(たとえば、スクリーンによる水切り)を通過することにより、一部の水分の除去が行われた後、含水クラムの状態(すなわち、水を含むクラムの状態)あるいはクラムスラリーの状態にて、押出機1のフィード口310に連続的に供給されるようになっている。なお、含水クラムの状態である場合には、水を同伴するものであってもよい。そして、押出機1のフィード口310に供給された含水クラムあるいはクラムスラリーは、後述するように、押出機1内にて、乾燥が行われることとなる。なお、本実施形態によれば、図1に示すように、洗浄タンク7による洗浄および押出機1による乾燥を連続工程で行うものであるため、省スペース化および生産効率の向上を可能とすることができ、さらには、連続工程で行うことにより、製造安定性を高めることもできる。
As shown in FIG. 1, the manufacturing apparatus according to the present embodiment includes an extruder 1 and a cleaning tank 7. As shown in FIG. 1, the crumb slurry obtained according to the above method is continuously supplied to the washing tank 7, and the water-containing crumb contained in the crumb slurry is washed in the washing tank 7. In the washing tank 7, the washed clam slurry (more specifically, the clam slurry containing the washed hydrous crumb) is continuously discharged from the washing tank 7, and the continuously discharged clam slurry (more specifically). Specifically, the clam slurry containing the washed hydrous crumb) is continuously supplied to the feed port 310 of the extruder 1 from the discharge port provided in the washing tank 7. More specifically, the washed crumb slurry is continuously discharged from the discharge port provided in the washing tank 7 and passes through the water removal facility 8 (for example, draining by a screen) shown in FIG. After some water has been removed, it is continuously supplied to the feed port 310 of the extruder 1 in the state of a hydrous crumb (that is, the state of a crumb containing water) or the state of a crumb slurry. It has become. If it is in the state of a hydrous crumb, it may be accompanied by water. Then, the hydrous crumb or the crumb slurry supplied to the feed port 310 of the extruder 1 is dried in the extruder 1 as described later. According to the present embodiment, as shown in FIG. 1, cleaning by the cleaning tank 7 and drying by the extruder 1 are performed in a continuous process, so that space saving and improvement of production efficiency are possible. Furthermore, it is possible to improve the production stability by performing it in a continuous process.
洗浄タンク7による、クラムスラリー(より具体的には、クラムスラリー中に含まれる含水クラム)の洗浄方法としては、特に限定されないが、洗浄タンク7に、クラムスラリーとともに、洗浄水を供給し、洗浄タンク7に備えられた攪拌羽根により攪拌する方法が挙げられる。これにより、アクリルゴムのクラム中における、凝固に用いた凝固剤の含有量を低減することができる。クラム100重量部に対する、洗浄水の供給量は、洗浄を効果的に行うという観点より、好ましくは900~9900重量部、より好ましくは1570~4900重量部である。なお、図1においては、洗浄タンク7を一つ備える態様を例示したが、2以上の洗浄タンクを多段に設けた構成として、複数回の洗浄を行うような態様としてもよい。
The method for cleaning the clam slurry (more specifically, the water-containing crumb contained in the clam slurry) by the cleaning tank 7 is not particularly limited, but the cleaning tank 7 is supplied with cleaning water together with the clam slurry for cleaning. A method of stirring by a stirring blade provided in the tank 7 can be mentioned. As a result, the content of the coagulant used for coagulation in the acrylic rubber crumb can be reduced. The amount of washing water supplied with respect to 100 parts by weight of the crumb is preferably 900 to 9900 parts by weight, more preferably 1570 to 4900 parts by weight, from the viewpoint of effectively performing washing. In addition, although the embodiment in which one cleaning tank 7 is provided is illustrated in FIG. 1, the embodiment in which two or more cleaning tanks are provided in multiple stages may be configured to perform cleaning a plurality of times.
押出機1は、図1に示すように、駆動ユニット2、および分割された11個のバレルブロック31~41で構成される単一のバレル3を有する。バレル3の内部には、供給ゾーン100、脱水ゾーン102、および乾燥ゾーン104が、バレル3の上流側から下流側にかけて順次形成されている。
As shown in FIG. 1, the extruder 1 has a drive unit 2 and a single barrel 3 composed of 11 divided barrel blocks 31 to 41. Inside the barrel 3, a supply zone 100, a dehydration zone 102, and a drying zone 104 are sequentially formed from the upstream side to the downstream side of the barrel 3.
供給ゾーン100は、洗浄タンク7から連続的に供給される含水クラムあるいはクラムスラリーをバレル3の内部に供給する領域である。脱水ゾーン102は、含水クラムあるいはクラムスラリーから、凝固剤などが含まれる液体(セラム水)を分離し排出する領域である。乾燥ゾーン104は、脱水後のクラムを乾燥させる領域である。
The supply zone 100 is a region for supplying the hydrous crumb or the crumb slurry continuously supplied from the cleaning tank 7 to the inside of the barrel 3. The dehydration zone 102 is a region for separating and discharging a liquid (serum water) containing a coagulant or the like from the hydrous crumb or crumb slurry. The drying zone 104 is a region for drying the dehydrated crumbs.
本実施形態では、バレルブロック31の内部が供給ゾーン100に対応し、バレルブロック32~34の内部が脱水ゾーン102に対応し、バレルブロック35~41の内部が乾燥ゾーン104に対応する。なお、各バレルブロックの設置数は、取り扱うアクリルゴムの組成等に応じて最適な数とすることができ、図1に示す態様に限定されるものではない。
In the present embodiment, the inside of the barrel block 31 corresponds to the supply zone 100, the inside of the barrel blocks 32 to 34 corresponds to the dehydration zone 102, and the inside of the barrel blocks 35 to 41 corresponds to the drying zone 104. The number of barrel blocks installed can be optimized according to the composition of the acrylic rubber to be handled, and is not limited to the mode shown in FIG.
供給ゾーン100を構成するバレルブロック31には、含水クラムあるいはクラムスラリーを受け入れるフィード口310が形成され、フィード口310に、洗浄タンク7から、スクリーン8を介して、一部の水分の除去された、含水クラムあるいはクラムスラリーが連続的に供給される。また、脱水ゾーン102を構成するバレルブロック32,34には、含水クラムに含まれる水分を排水する第1排出スリット320、第2排出スリット340が、それぞれ形成されている。また、乾燥ゾーン104の一部を構成するバレルブロック36,38,39,40には、脱水後のクラム中に含まれる水分などの揮発分を脱気により除去するための第1減圧ベント口360、第2減圧ベント口380、第3減圧ベント口390、および第4減圧ベント口400がそれぞれ形成されている。
A feed port 310 for receiving a water-containing crumb or a crumb slurry was formed in the barrel block 31 constituting the supply zone 100, and a part of water was removed from the washing tank 7 through the screen 8 in the feed port 310. , Hydrous crumbs or crumb slurries are continuously fed. Further, the barrel blocks 32 and 34 forming the dehydration zone 102 are formed with a first discharge slit 320 and a second discharge slit 340 for draining the water contained in the water-containing crumb, respectively. Further, in the barrel blocks 36, 38, 39, 40 which form a part of the drying zone 104, the first decompression vent port 360 for removing volatile substances such as water contained in the crumb after dehydration by degassing. , The second decompression vent port 380, the third decompression vent port 390, and the fourth decompression vent port 400 are formed, respectively.
図2は、押出機1の内部に配置されるスクリューを示す概略図である。バレル3の内部には、図2に示すようなスクリュー6が配置されている。スクリュー6の基端には、これを駆動するために、駆動ユニット2(図1参照)に格納されたモータなどの駆動手段が接続されており、これによりスクリュー6は回転駆動自在に保持される。スクリュー6の形状は、特に限定されないが、多種のスクリュー構成を持つスクリューブロックとニーディングディスクとを適宜組合せて構成することが好適である。
FIG. 2 is a schematic view showing a screw arranged inside the extruder 1. A screw 6 as shown in FIG. 2 is arranged inside the barrel 3. A drive means such as a motor housed in a drive unit 2 (see FIG. 1) is connected to the base end of the screw 6 in order to drive the screw 6, whereby the screw 6 is rotatably held. .. The shape of the screw 6 is not particularly limited, but it is preferable to appropriately combine a screw block having various screw configurations and a kneading disc.
本実施形態では、スクリュー6が、バレル3の内部に形成された上述した各ゾーン100,102,104に対応する領域に、それぞれ異なる態様のスクリュー構成を有するように構成することができる。
In the present embodiment, the screw 6 can be configured to have different screw configurations in the regions corresponding to the zones 100, 102, and 104 described above formed inside the barrel 3.
本実施形態では、図2に示すように、スクリュー6全体の長さをL(mm)とし、スクリュー6の外径をDa(mm)とした場合に、L/Daは、好ましくは20~60である。なお、スクリュー6の外径Daは、スクリューを構成するスクリューブロック60の山部60A(図3参照)の、軸方向から見た場合における直径で定義される。
In the present embodiment, as shown in FIG. 2, when the total length of the screw 6 is L (mm) and the outer diameter of the screw 6 is Da (mm), the L / Da is preferably 20 to 60. Is. The outer diameter Da of the screw 6 is defined by the diameter of the peak portion 60A (see FIG. 3) of the screw block 60 constituting the screw when viewed from the axial direction.
また、図3に示すように、本実施形態では、このようなスクリュー6を2本用いて、軸芯を平行にして互いに噛み合った状態とした二軸押出機としている。ここで、図3は、図1のIII-III線と図2のIII-III線に沿う断面図であり、図3に示す断面図は、押出機1のスクリューブロック60部分の断面図であって、谷部60Bを横切る断面図である。すなわち、図3に示すように、2本のスクリュー6,6は、一方のスクリュー6のスクリューブロック60の山部60Aを、他方のスクリュー6のスクリューブロック60の谷部60Bに噛み合わせるとともに、一方のスクリュー6のスクリューブロック60の谷部60Bを、他方のスクリュー6のスクリューブロック60の山部60Aに噛み合わせる状態とした二軸噛合型である。二軸噛合型とすることにより、各ゾーン100,102,104における混合性を向上させることができる。また、2本のスクリュー6の回転方向は、同方向でも異方向でもよいが、セルフクリーニングの性能面からは同方向に回転する形式のものが好ましい。
Further, as shown in FIG. 3, in the present embodiment, two such screws 6 are used to form a twin-screw extruder in which the shaft cores are parallel to each other and meshed with each other. Here, FIG. 3 is a cross-sectional view taken along the lines III-III of FIG. 1 and the line III-III of FIG. 2, and the cross-sectional view shown in FIG. 3 is a cross-sectional view of the screw block 60 portion of the extruder 1. It is sectional drawing which crosses the valley part 60B. That is, as shown in FIG. 3, the two screws 6 and 6 mesh the peak portion 60A of the screw block 60 of one screw 6 with the valley portion 60B of the screw block 60 of the other screw 6 and one of them. This is a biaxial meshing type in which the valley portion 60B of the screw block 60 of the screw 6 of the screw 6 is engaged with the peak portion 60A of the screw block 60 of the other screw 6. By adopting the biaxial meshing type, the mixing property in each zone 100, 102, 104 can be improved. Further, the rotation directions of the two screws 6 may be the same direction or different directions, but from the viewpoint of self-cleaning performance, a type that rotates in the same direction is preferable.
図3に示すように、本実施形態では、スクリューブロック60の外径をDa(mm)、スクリューブロック60の谷部60Bの短径をDi(mm)とした場合に、Da/Diが、好ましくは1.2~2.5の範囲である。Da/Diをこのような範囲とすることで、設備を大がかりなものとすることなく、アクリルゴムの回収率や生産レート(単位時間あたりに得られる乾燥されたアクリルゴムの量)を良好なものとすることができる。
As shown in FIG. 3, in the present embodiment, when the outer diameter of the screw block 60 is Da (mm) and the minor diameter of the valley portion 60B of the screw block 60 is Di (mm), Da / Di is preferable. Is in the range of 1.2 to 2.5. By setting Da / Di in such a range, the recovery rate and production rate of acrylic rubber (the amount of dried acrylic rubber obtained per unit time) can be improved without making the equipment large-scale. Can be.
また、谷部60Bの短径Diは、図3に示すように、谷部60Bのうち、谷部60Bの深さが、最も深くなっている部分である深さDi’(mm)である部分における、軸方向から見た場合における径である。すなわち、谷部60Bの短径Diは、外径Da、および谷部60Bのうち深さが最も深い部分である深さDi’から、Di=Da-Di’×2により求めることができる。
Further, as shown in FIG. 3, the minor diameter Di of the valley portion 60B is a portion of the valley portion 60B in which the depth of the valley portion 60B is the deepest portion, which is the depth Di'(mm). Is the diameter when viewed from the axial direction. That is, the minor diameter Di of the valley portion 60B can be obtained from the outer diameter Da and the depth Di'which is the deepest portion of the valley portion 60B by Di = Da-Di'x2.
また、スクリュー6のうち、乾燥ゾーン104に対応する領域の軸方向の長さをL1(mm)とした場合に、L1と、上述したスクリュー6全体の長さをL(mm)との関係L1/Lは、好ましくは0.2~0.9である。L1/Lがこの範囲であると、押出乾燥の条件制御が容易で、アクリルゴムが十分に乾燥されるとともに、アクリルゴムの劣化の抑制が可能となるため、安定してアクリルゴムの製造を行うことができる。
Further, when the axial length of the region corresponding to the drying zone 104 of the screw 6 is L1 (mm), the relationship between L1 and the entire length of the screw 6 described above is L (mm) L1. / L is preferably 0.2 to 0.9. When L1 / L is in this range, the conditions for extrusion drying can be easily controlled, the acrylic rubber can be sufficiently dried, and the deterioration of the acrylic rubber can be suppressed. Therefore, the acrylic rubber can be stably produced. be able to.
なお、本実施形態では、上述したバレルブロック41の下流側には、バレル3内で脱水・乾燥処理されたアクリルゴムを、所定形状に押し出し製品化するためのダイ5が接続され、たとえば、乾燥されたアクリルゴムをシート状に押出すことができる。
In the present embodiment, a die 5 for extruding the acrylic rubber dehydrated and dried in the barrel 3 into a predetermined shape and commercializing it is connected to the downstream side of the barrel block 41 described above, for example, drying. The acrylic rubber can be extruded into a sheet.
次に、本実施形態に係る押出機1を用いたアクリルゴムの製造方法を説明する。
まず、洗浄タンク7により洗浄されたクラムスラリーを、図1に示すように、水除去設備8(たとえば、スクリーンによる水切り)を通過させることにより、一部の水分の除去を行い、アクリルゴムのクラムを、一部の水分の除去が行われた、含水クラムの状態あるいはクラムスラリーの状態で、バレルブロック31に設けられたフィード口310に連続的に供給する。あるいは、洗浄タンク7により洗浄されたクラムスラリーを、洗浄タンク7から、直接(あるいは、所定のクラムスラリー流路を介して)、バレルブロック31に設けられたフィード口310に連続的に供給してもよい。フィード口310に供給する含水クラムあるいはクラムスラリー中に含まれるクラム状のアクリルゴムとしては、最終的に得られる乾燥後のアクリルゴム中に含まれる凝固剤量を低く抑えることができるという観点、および後述する第1排出スリット320からの、クラムのスリット抜けを低減できるという観点から、含水率が比較的高いものとすることが好ましく、具体的には、フィード口310に供給するクラムの含水率は、好ましくは50~70重量%であり、より好ましくは58~70重量%であり、さらに好ましくは60~70重量%である。なお、フィード口310に供給するクラムの含水率は、たとえば、洗浄タンク7に供給する洗浄前のクラムスラリーの含水率や、洗浄タンク7に供給する洗浄水の量や、スリット・スクリーン等の水除去設備8を経て調整することで、制御することができる。 Next, a method for producing acrylic rubber using theextruder 1 according to the present embodiment will be described.
First, as shown in FIG. 1, the crumb slurry washed by thewashing tank 7 is passed through a water removing facility 8 (for example, draining with a screen) to remove a part of water, and the acrylic rubber crumb is used. Is continuously supplied to the feed port 310 provided in the barrel block 31 in the state of a water-containing crumb or a crumb slurry in which a part of water has been removed. Alternatively, the clam slurry washed by the washing tank 7 is continuously supplied from the washing tank 7 directly (or via a predetermined clam slurry flow path) to the feed port 310 provided in the barrel block 31. May be good. As the crumb-shaped acrylic rubber contained in the hydrous crumb or the crumb slurry supplied to the feed port 310, the amount of the coagulant contained in the finally obtained dried acrylic rubber can be suppressed to a low level, and From the viewpoint of reducing the slipping out of the crumb from the first discharge slit 320, which will be described later, it is preferable that the water content is relatively high. Specifically, the water content of the crumb supplied to the feed port 310 is , It is preferably 50 to 70% by weight, more preferably 58 to 70% by weight, and even more preferably 60 to 70% by weight. The water content of the clam supplied to the feed port 310 includes, for example, the water content of the clam slurry before cleaning supplied to the cleaning tank 7, the amount of cleaning water supplied to the cleaning tank 7, and water such as a slit screen. It can be controlled by adjusting through the removal equipment 8.
まず、洗浄タンク7により洗浄されたクラムスラリーを、図1に示すように、水除去設備8(たとえば、スクリーンによる水切り)を通過させることにより、一部の水分の除去を行い、アクリルゴムのクラムを、一部の水分の除去が行われた、含水クラムの状態あるいはクラムスラリーの状態で、バレルブロック31に設けられたフィード口310に連続的に供給する。あるいは、洗浄タンク7により洗浄されたクラムスラリーを、洗浄タンク7から、直接(あるいは、所定のクラムスラリー流路を介して)、バレルブロック31に設けられたフィード口310に連続的に供給してもよい。フィード口310に供給する含水クラムあるいはクラムスラリー中に含まれるクラム状のアクリルゴムとしては、最終的に得られる乾燥後のアクリルゴム中に含まれる凝固剤量を低く抑えることができるという観点、および後述する第1排出スリット320からの、クラムのスリット抜けを低減できるという観点から、含水率が比較的高いものとすることが好ましく、具体的には、フィード口310に供給するクラムの含水率は、好ましくは50~70重量%であり、より好ましくは58~70重量%であり、さらに好ましくは60~70重量%である。なお、フィード口310に供給するクラムの含水率は、たとえば、洗浄タンク7に供給する洗浄前のクラムスラリーの含水率や、洗浄タンク7に供給する洗浄水の量や、スリット・スクリーン等の水除去設備8を経て調整することで、制御することができる。 Next, a method for producing acrylic rubber using the
First, as shown in FIG. 1, the crumb slurry washed by the
また、フィード口310に供給する含水クラムあるいはクラムスラリー中に含まれるクラム状のアクリルゴムの平均クラム径は、特に限定されないが、乾燥効率を高めるという観点から、好ましくは0.1~10mmであり、より好ましくは1.0~5.0mmである。クラム状のアクリルゴムの平均クラム径は、凝固時の凝固条件を調整することにより制御することができる。フィード口310に供給する含水クラムあるいはクラムスラリーの温度は、乾燥効率を十分なものとするという観点より、好ましくは30~90℃であり、より好ましくは40~90℃、さらに好ましくは50~85℃である。フィード口310に供給する含水クラムあるいはクラムスラリーの温度は、アクリルゴムの重合温度、凝固に用いる凝固剤の温度(例えば凝固剤水溶液の温度)、洗浄タンク7により洗浄を行う際の洗浄水の温度などを調整することにより制御することができる。
The average crumb diameter of the crumb-shaped acrylic rubber contained in the hydrous crumb or the crumb slurry supplied to the feed port 310 is not particularly limited, but is preferably 0.1 to 10 mm from the viewpoint of improving the drying efficiency. , More preferably 1.0 to 5.0 mm. The average crumb diameter of the crumb-shaped acrylic rubber can be controlled by adjusting the solidification conditions at the time of solidification. The temperature of the hydrous crumb or the crumb slurry supplied to the feed port 310 is preferably 30 to 90 ° C., more preferably 40 to 90 ° C., still more preferably 50 to 85, from the viewpoint of ensuring sufficient drying efficiency. ℃. The temperature of the hydrous crumb or crumb slurry supplied to the feed port 310 is the polymerization temperature of acrylic rubber, the temperature of the coagulant used for coagulation (for example, the temperature of the coagulant aqueous solution), and the temperature of the washing water when washing by the washing tank 7. It can be controlled by adjusting such as.
供給ゾーン100を構成するバレルブロック31におけるバレル温度は、特に限定されないが、アクリルゴムの劣化を抑制しつつ、乾燥効率を高めるという観点より、好ましくは30~150℃、より好ましくは40~140℃である。
The barrel temperature in the barrel block 31 constituting the supply zone 100 is not particularly limited, but is preferably 30 to 150 ° C., more preferably 40 to 140 ° C. from the viewpoint of improving the drying efficiency while suppressing the deterioration of the acrylic rubber. Is.
フィード口310に供給された含水クラムあるいはクラムスラリーは、スクリュー6の回転により、供給ゾーン100から、脱水ゾーン102に送られる。脱水ゾーン102では、バレルブロック32に設けられた第1排出スリット320、およびバレルブロック34に設けられた第2排出スリット340から、含水クラムあるいはクラムスラリーに含まれるセラム水(より具体的には、クラムから分離されたセラム水)を排出させ、含水状態のクラムを、好ましくは10~50重量%の水分を含有する状態で、より好ましくは10~40重量%の水分を含有する状態で得ることができる。
The hydrous crumb or crumb slurry supplied to the feed port 310 is sent from the supply zone 100 to the dehydration zone 102 by the rotation of the screw 6. In the dehydration zone 102, from the first discharge slit 320 provided in the barrel block 32 and the second discharge slit 340 provided in the barrel block 34, the water-containing crumb or serum water contained in the crumb slurry (more specifically, more specifically, (Serum water separated from the crumbs) is discharged to obtain a hydrous crumb in a state of preferably containing 10 to 50% by weight of water, more preferably 10 to 40% by weight of water. Can be done.
脱水ゾーン102を構成するバレルブロック32~34におけるバレル温度は、特に限定されないが、アクリルゴムの劣化を抑制しつつ、脱水効率を高めるという観点より、好ましくは30~170℃、より好ましくは40~160℃である。
The barrel temperature in the barrel blocks 32 to 34 constituting the dehydration zone 102 is not particularly limited, but is preferably 30 to 170 ° C., more preferably 40 to 170 ° C. from the viewpoint of increasing the dehydration efficiency while suppressing the deterioration of the acrylic rubber. It is 160 ° C.
脱水ゾーン102で得られた含水状態のクラムは、スクリュー6の回転により乾燥ゾーン104に送られる。乾燥ゾーン104に送られたクラムは、スクリュー6の回転により可塑化混練されて融体となり、発熱して昇温しながら下流側へ運ばれる。そして、この融体がバレルブロック36,38,39,40に設けられた減圧ベント口360,380,390,400に達すると、圧力が解放されるために、融体中に含まれる水分などの揮発分が分離気化される。
The water-containing crumb obtained in the dehydration zone 102 is sent to the drying zone 104 by the rotation of the screw 6. The crumb sent to the drying zone 104 is plasticized and kneaded by the rotation of the screw 6 to form a melt, which generates heat and is carried to the downstream side while raising the temperature. Then, when the melt reaches the decompression vent ports 360, 380, 390, 400 provided in the barrel blocks 36, 38, 39, 40, the pressure is released, so that the moisture contained in the melt is released. Volatile matter is separated and vaporized.
減圧ベント口360,380,390,400は、図1に示すように、各減圧ベント口の側面に接続された減圧配管を介して、減圧ポンプに接続されており、これにより、減圧されるように構成されている。また、減圧ベント口360,380,390,400には、絶対圧力を調整するためのバルブ(不図示)および絶対圧力を測定するための圧力計(不図示)が設けられており、これにより、絶対圧力を調整できるようになっている。なお、図1においては、減圧ベント口360,380,390,400は、減圧配管を通して、同一の減圧ポンプに接続されるような態様を例示したが、このような態様に特に限定されず、別々の減圧ポンプに接続してもよい。
As shown in FIG. 1, the decompression vent ports 360, 380, 390, and 400 are connected to a decompression pump via a decompression pipe connected to the side surface of each decompression vent port so that the pressure is reduced. It is configured in. Further, the decompression vent ports 360, 380, 390, and 400 are provided with a valve (not shown) for adjusting the absolute pressure and a pressure gauge (not shown) for measuring the absolute pressure. The absolute pressure can be adjusted. In addition, in FIG. 1, the decompression vent ports 360, 380, 390, and 400 are illustrated as being connected to the same decompression pump through a decompression pipe, but the present invention is not particularly limited to such an embodiment and is separate. May be connected to a decompression pump.
本実施形態においては、減圧ベント口360,380,390,400の最も上流側に位置する第1減圧ベント口360の絶対圧力P1を、最も下流側に位置する第4減圧ベント口400の絶対圧力P4よりも高い(P1>P4)ものとする。これにより、スクリュー6の回転により可塑化混練されて融体となったアクリルゴムのベントアップ(アクリルゴムの融体が発泡し、減圧ベント口に、アクリルゴムの融体が流れ込む現象)を抑制しながら、減圧ベント口360,380,390,400による、アクリルゴムの融体中に含まれる水分などの揮発分の除去効率を適切に高めることができるものである。
In the present embodiment, the absolute of the fourth vacuum vent 400 positioned absolute pressure P 1 of the first vacuum vent port 360 which is located on the most upstream side of the vacuum vent port 360,380,390,400, on the most downstream side It shall be higher than the pressure P 4 (P 1 > P 4 ). As a result, the vent-up of acrylic rubber that has been plasticized and kneaded by the rotation of the screw 6 to form a melt (a phenomenon in which the melt of acrylic rubber foams and the melt of acrylic rubber flows into the decompression vent port) is suppressed. However, the efficiency of removing volatile components such as water contained in the melt of acrylic rubber can be appropriately increased by the decompression vent ports 360, 380, 390, 400.
本実施形態では、第1減圧ベント口360の絶対圧力P1を、第4減圧ベント口400の絶対圧力P4よりも高い(P1>P4)ものとすればよいが(すなわち、最も上流側の減圧ベント口の絶対圧力を、最も下流側の減圧ベンド口の絶対圧力よりも高いものとすればよいが)、これらの圧力の差を、5.0~94.0kPaの範囲とすることが好ましく、9.0~92.0kPaの範囲とすることがより好ましく、18.0~88.0kPaの範囲とすることがさらに好ましい。圧力の差を上記範囲とすることにより、ベントアップを適切に抑制しながら、アクリルゴムの融体中に含まれる水分などの揮発分の除去効率をより高めることができる。特に、押出乾燥時のアクリルゴムの粘度等を考慮すると、圧力の差を上記範囲とすることが好適である。なお、以下、第1減圧ベント口360の絶対圧力P1は、最も上流側の減圧ベント口の絶対圧力を表し、第4減圧ベント口400の絶対圧力P4は、最も下流側の減圧ベント口の絶対圧力を表す。
In the present embodiment, the absolute pressure P 1 of the first decompression vent port 360 may be higher than the absolute pressure P 4 of the fourth decompression vent port 400 (P 1 > P 4 ) (that is, the most upstream). The absolute pressure of the decompression vent port on the side may be higher than the absolute pressure of the decompression bend port on the most downstream side), and the difference between these pressures shall be in the range of 5.0 to 94.0 kPa. The range is preferably 9.0 to 92.0 kPa, more preferably 18.0 to 88.0 kPa. By setting the pressure difference within the above range, it is possible to further improve the efficiency of removing volatile substances such as water contained in the melt of acrylic rubber while appropriately suppressing vent-up. In particular, considering the viscosity of acrylic rubber during extrusion drying, it is preferable to set the pressure difference within the above range. Hereinafter, the absolute pressure P 1 of the first decompression vent port 360 represents the absolute pressure of the most upstream decompression vent port, and the absolute pressure P 4 of the fourth decompression vent port 400 is the most downstream decompression vent port. Represents the absolute pressure of.
なお、本実施形態おいては、第1減圧ベント口360の絶対圧力P1を、第4減圧ベント口400の絶対圧力P4よりも高い(P1>P4)ものとすればよく、各減圧ベント口の絶対圧力は、特に限定されないが、第1減圧ベント口360の絶対圧力は、7.3~96.3kPaとすることが好ましく、11.3~94.3kPaとすることがより好ましく、21.3~91.3kPaとすることがさらに好ましい。
In the present embodiment, the absolute pressure P 1 of the first decompression vent port 360 may be higher than the absolute pressure P 4 of the fourth decompression vent port 400 (P 1 > P 4 ). The absolute pressure of the decompression vent port is not particularly limited, but the absolute pressure of the first decompression vent port 360 is preferably 7.3 to 96.3 kPa, more preferably 11.3 to 94.3 kPa. It is more preferably 21.3 to 91.3 kPa.
また、本実施形態おいては、第1減圧ベント口360の絶対圧力P1が、第4減圧ベント口400の絶対圧力P4よりも高いものであればよく、第2減圧ベント口380の絶対圧力P2および第3減圧ベント口390の絶対圧力P3は、特に限定されないが、第2減圧ベント口380の絶対圧力P2は、第1減圧ベント口360の絶対圧力P1と同じ(P1=P2)か、第2減圧ベント口380の絶対圧力P2の方が低い(P1>P2)ような態様とすることが好ましい。また、第3減圧ベント口390の絶対圧力P3も、特に限定されないが、第2減圧ベント口380の絶対圧力P2との関係において、第2減圧ベント口380の絶対圧力P2と同じ(P2=P3)か、第3減圧ベント口390の絶対圧力P3の方が低い(P2>P3)ような態様とすることが好ましい。さらには、第3減圧ベント口390の絶対圧力P3は、第4減圧ベント口400の絶対圧力P4との関係において、第4減圧ベント口400の絶対圧力P4と同じ(P3=P4)か、第3減圧ベント口390の絶対圧力P3の方が高い(P3>P4)ような態様とすることが好ましい。
Also, keep this embodiment, an absolute pressure P 1 of the first vacuum vent port 360, as long as greater than the absolute pressure P 4 of the fourth vacuum vent 400, the absolute of the second vacuum vent port 380 The absolute pressure P 2 and the absolute pressure P 3 of the third decompression vent port 390 are not particularly limited, but the absolute pressure P 2 of the second decompression vent port 380 is the same as the absolute pressure P 1 of the first decompression vent port 360 (P). It is preferable that 1 = P 2 ) or the absolute pressure P 2 of the second decompression vent port 380 is lower (P 1 > P 2 ). Further, the absolute pressure P 3 of the third decompression vent port 390 is also not particularly limited, but is the same as the absolute pressure P 2 of the second decompression vent port 380 in relation to the absolute pressure P 2 of the second decompression vent port 380 ( It is preferable that P 2 = P 3 ) or the absolute pressure P 3 of the third decompression vent port 390 is lower (P 2 > P 3 ). Furthermore, an absolute pressure P 3 of the third vacuum vent port 390, in relation to the absolute pressure P 4 of the fourth vacuum vent 400, the same as the absolute pressure P 4 of the fourth vacuum vent 400 (P 3 = P 4 ) Or, it is preferable that the absolute pressure P 3 of the third decompression vent port 390 is higher (P 3 > P 4 ).
すなわち、本実施形態においては、各減圧ベント口の絶対圧力P1,P2,P3,P4について、P1>P2=P3=P4の関係、P1=P2>P3=P4の関係、P1=P2=P3>P4の関係、P1>P2>P3=P4の関係、P1>P2=P3>P4の関係、および、P1>P2>P3>P4の関係のいずれかとすることが好ましい。
That is, in the present embodiment, for the absolute pressures P 1 , P 2 , P 3 , and P 4 of each decompression vent port, the relationship of P 1 > P 2 = P 3 = P 4 , P 1 = P 2 > P 3 = P 4 relationship, P 1 = P 2 = P 3 > P 4 relationship, P 1 > P 2 > P 3 = P 4 relationship, P 1 > P 2 = P 3 > P 4 relationship, and It is preferable that the relationship is P 1 > P 2 > P 3 > P 4 .
これらの中でも、アクリルゴムの融体中に含まれる水分などの揮発分の除去効率をより高めることができるという観点より、4つの減圧ベント口のうち、3つの減圧ベント口に着目した場合に、このような3つの減圧ベント口の絶対圧力が、押出方向上流側から、下流側に向かって、順に低くなるような態様とすることが好ましい。すなわち、4つの減圧ベント口のうち、第1減圧ベント口360、第2減圧ベント口380、および第4減圧ベント口400に着目した場合には、これらの絶対圧力P1,P2,P4について、P1>P2>P4の関係(すなわち、P1>P2>P3=P4の関係、またはP1>P2>P3>P4の関係)とすることが好ましい。また、4つの減圧ベント口のうち、第1減圧ベント口360、第3減圧ベント口390、および第4減圧ベント口400に着目した場合には、これらの絶対圧力P1,P3,P4について、P1>P3>P4の関係(すなわち、P1>P2=P3>P4の関係、またはP1>P2>P3>P4の関係)とすることが好ましい。この場合においては、P1>P2>P3>P4の関係のように、4つの減圧ベント口の絶対圧力が、押出方向上流側から、下流側に向かって、順に低くなるような態様とすることも、もちろん可能である。
Among these, from the viewpoint of being able to further improve the efficiency of removing volatile substances such as water contained in the melt of acrylic rubber, when focusing on three of the four decompression vent ports, It is preferable that the absolute pressures of the three decompression vent ports decrease in order from the upstream side in the extrusion direction to the downstream side. That is, when focusing on the first decompression vent port 360, the second decompression vent port 380, and the fourth decompression vent port 400 among the four decompression vent ports, these absolute pressures P 1 , P 2 , P 4 It is preferable that the relationship is P 1 > P 2 > P 4 (that is, P 1 > P 2 > P 3 = P 4 or P 1 > P 2 > P 3 > P 4 ). Further, when focusing on the first decompression vent port 360, the third decompression vent port 390, and the fourth decompression vent port 400 among the four decompression vent ports, these absolute pressures P 1 , P 3 , P 4 It is preferable that the relationship is P 1 > P 3 > P 4 (that is, P 1 > P 2 = P 3 > P 4 or P 1 > P 2 > P 3 > P 4 ). In this case, the absolute pressures of the four decompression vent ports decrease in order from the upstream side in the extrusion direction to the downstream side, as in the relationship of P 1 > P 2 > P 3 > P 4. Of course, it is also possible.
各減圧ベント口の絶対圧力は、上記関係となるように適宜設定すればよく、特に限定されないが、第2減圧ベント口370の絶対圧力は、2.3~91.3kPaとすることが好ましく、6.3~81.3kPaとすることがより好ましく、11.3~71.3kPaとすることがさらに好ましい。また、第3減圧ベント口380の絶対圧力は、2.3~61.3kPaとすることが好ましく、3.3~51.3kPaとすることがより好ましく、3.3~46.3kPaとすることがさらに好ましく、第4減圧ベント口400の絶対圧力は、2.3~51.3kPaとすることが好ましく、3.3~41.3kPaとすることがより好ましく、3.3~36.3kPaとすることがさらに好ましい。
The absolute pressure of each decompression vent port may be appropriately set so as to have the above relationship, and is not particularly limited, but the absolute pressure of the second decompression vent port 370 is preferably 2.3 to 91.3 kPa. It is more preferably 6.3 to 81.3 kPa, and even more preferably 11.3 to 71.3 kPa. The absolute pressure of the third decompression vent port 380 is preferably 2.3 to 61.3 kPa, more preferably 3.3 to 51.3 kPa, and 3.3 to 46.3 kPa. The absolute pressure of the fourth decompression vent port 400 is preferably 2.3 to 51.3 kPa, more preferably 3.3 to 41.3 kPa, and 3.3 to 36.3 kPa. It is more preferable to do so.
なお、たとえば、第4減圧ベント口400の絶対圧力を、好ましくは2.3~21.3kPa、より好ましくは2.3~11.3kPaと比較的低いものとする場合には、第1減圧ベント口360の絶対圧力P1と、第4減圧ベント口400の絶対圧力P4との圧力の差を、60~94.0kPaの範囲とすることが好ましく、より好ましくは70~94.0kPa、さらに好ましくは80~88.0kPaである。また、たとえば、第4減圧ベント口400の絶対圧力を、好ましくは22.3~51.3kPa、より好ましくは26.3~41.3kPa、さらに好ましくは28.3~36.3kPaと比較的高いものとする場合には、第1減圧ベント口360の絶対圧力P1と、第4減圧ベント口400の絶対圧力P4との圧力の差を、5.0~25kPaの範囲とすることが好ましく、より好ましくは5.0~20kPa、さらに好ましくは7.0~15kPaである。圧力の差を、上記範囲とすることにより、アクリルゴムの押出乾燥により適した条件とすることができ、これにより、ベントアップの抑制効果およびアクリルゴムの融体中に含まれる水分などの揮発分の除去効率をより高めることができる。
For example, when the absolute pressure of the fourth decompression vent port 400 is relatively low, preferably 2.3 to 21.3 kPa, more preferably 2.3 to 11.3 kPa, the first decompression vent the absolute pressure P 1 of the mouth 360, the difference in pressure between the absolute pressure P 4 of the fourth vacuum vent 400, preferably in the range of 60 ~ 94.0kPa, more preferably 70 ~ 94.0kPa, further It is preferably 80 to 88.0 kPa. Further, for example, the absolute pressure of the fourth decompression vent port 400 is relatively high, preferably 22.3 to 51.3 kPa, more preferably 26.3 to 41.3 kPa, and even more preferably 28.3 to 36.3 kPa. when a thing is, the absolute pressure P 1 of the first vacuum vent port 360, that the difference in pressure between the absolute pressure P 4 of the fourth vacuum vent port 400, in the range of 5.0 ~ 25 kPa preferably , More preferably 5.0 to 20 kPa, still more preferably 7.0 to 15 kPa. By setting the pressure difference within the above range, it is possible to make the conditions more suitable for extrusion drying of the acrylic rubber, thereby suppressing the vent-up effect and volatile components such as water contained in the melt of the acrylic rubber. Removal efficiency can be further improved.
なお、図1に示すように、減圧ベント口360,380,390,400の上面には、減圧ベント内の様子を確認できるように、ガラス製の覗き窓361,381,391,401がそれぞれ形成されており、これにより、ベントアップの発生の有無を容易に確認でき、運転開始初期などの運転条件が安定しない段階おいてベントアップが発生した場合でも、このようなベントアップの発生を適時に発見することができる。
As shown in FIG. 1, glass viewing windows 361, 381, 391, 401 are formed on the upper surfaces of the decompression vent ports 360, 380, 390, and 400 so that the inside of the decompression vent can be confirmed. This makes it easy to confirm the presence or absence of vent-up, and even if vent-up occurs at a stage where the operating conditions are not stable, such as at the beginning of operation, such vent-up will occur in a timely manner. Can be found.
乾燥ゾーン104を構成するバレルブロック35~41におけるバレル温度は、特に限定されないが、アクリルゴムの融体のベントアップを適切に抑制しながら、アクリルゴムの融体中に含まれる水分などの揮発分の除去効率をより高めることが出来るという観点より、好ましくは100.0~220.0℃、より好ましくは105.0~210.0℃である。
The barrel temperature in the barrel blocks 35 to 41 constituting the drying zone 104 is not particularly limited, but volatile components such as water contained in the acrylic rubber melt while appropriately suppressing the vent-up of the acrylic rubber melt. From the viewpoint that the removal efficiency of the rubber can be further improved, the temperature is preferably 100.0 to 220.0 ° C, more preferably 105.0 to 210.0 ° C.
そして、乾燥ゾーン104を通過した水分が分離されたクラムは、スクリュー6により出口側へ送り出され、実質的に水分をほとんど含まない状態、具体的には、水分含有量が、好ましくは1.0重量%以下、より好ましくは0.1~0.8重量%と低減された状態でダイ5に導入され、ここで、たとえばシート状で排出され、必要に応じて冷却された後に、シートカッター(図示省略)に導入されて切断され、適当な長さとされる。
Then, the crumb from which the water has passed through the drying zone 104 is sent out to the outlet side by the screw 6, and is in a state of substantially containing almost no water, specifically, the water content is preferably 1.0. It is introduced into the die 5 in a state of being reduced to less than% by weight, more preferably 0.1 to 0.8% by weight, where it is discharged, for example, in the form of a sheet, cooled if necessary, and then a sheet cutter ( It is introduced into (not shown) and cut to an appropriate length.
なお、本実施形態においては、押出機1で単位時間当たりに乾燥されるアクリルゴムの処理量をQ[kg/h]、スクリュー6の回転数をN[rpm]としたとき、下記式(1)を満たすような条件とすることが好ましい。
3≦Q/N≦8 (1) In this embodiment, when the processing amount of acrylic rubber dried by theextruder 1 per unit time is Q [kg / h] and the rotation speed of the screw 6 is N [rpm], the following formula (1) ) Satisfying the conditions.
3 ≦ Q / N ≦ 8 (1)
3≦Q/N≦8 (1) In this embodiment, when the processing amount of acrylic rubber dried by the
3 ≦ Q / N ≦ 8 (1)
ここで、単位時間当たりに乾燥処理されるアクリルゴムの処理量Qは、押出機1において1回の押出乾燥処理が行われる場合に、1時間で乾燥処理されるアクリルゴムの処理量[kg/h]である。また、スクリュー6の回転数Nは、押出機1においてスクリュー6がバレル3の内部で1分間に回転したときの回転数[rpm]である。「Q/N」は、好ましくは3≦Q/N≦8であり、より好ましくは3.5≦Q/N≦7、さらに好ましくは4≦Q/N≦6、特に好ましくは4.5≦Q/N≦5.5である。
Here, the processing amount Q of the acrylic rubber to be dried per unit time is the processing amount [kg / kg / kg / kg / of acrylic rubber to be dried in one hour when the extrusion drying process is performed once in the extruder 1. h]. Further, the rotation speed N of the screw 6 is the rotation speed [rpm] when the screw 6 rotates inside the barrel 3 in 1 minute in the extruder 1. “Q / N” is preferably 3 ≦ Q / N ≦ 8, more preferably 3.5 ≦ Q / N ≦ 7, still more preferably 4 ≦ Q / N ≦ 6, and particularly preferably 4.5 ≦. Q / N ≦ 5.5.
本実施形態によれば、第1減圧ベント口360の絶対圧力P1を、第4減圧ベント口400の絶対圧力P4よりも高いものとするものであるため、「Q/N」を上記範囲とした場合でも、ベントアップを適切に抑制することができ、これにより、「Q/N」を上記範囲とすることによる効果、具体的には、含水率が適切に低減されたアクリルゴムを、高い生産性にて生産できるという効果を効果的に高めることができるものである。
According to this embodiment, the absolute pressure P 1 of the first vacuum vent port 360, because it is an higher than the absolute pressure P 4 of the fourth vacuum vent 400, a "Q / N" above range Even in the case of, the vent-up can be appropriately suppressed, and thus the effect of setting "Q / N" in the above range, specifically, the acrylic rubber in which the water content is appropriately reduced can be obtained. It is possible to effectively enhance the effect of being able to produce with high productivity.
以上のようにして、本実施形態の製造方法によれば、アクリルゴムを製造することができる。なお、本実施形態の製造方法により製造されるアクリルゴムのムーニー粘度(ML1+4、100℃)(ポリマームーニー)は、特に限定されないが、好ましくは10~80、より好ましくは20~70、さらに好ましくは25~60である。
As described above, according to the manufacturing method of the present embodiment, acrylic rubber can be manufactured. The Mooney viscosity (ML1 + 4, 100 ° C.) (polymer Mooney) of the acrylic rubber produced by the production method of the present embodiment is not particularly limited, but is preferably 10 to 80, more preferably 20 to 70, and even more preferably. It is 25 to 60.
以上のように、本発明によれば、第1の観点に係る発明として、
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機として、減圧ベント口を複数有するものを用い、
押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高くする、アクリルゴムの製造方法を提供することができる。
本発明の第1の観点に係る発明によれば、ベントアップの発生を抑制しながら、アクリルゴムの含水率を適切に低減することができる。
なお、本発明の第1の観点に係る発明において、減圧ベント口が3個以上ある場合には、3個以上ある減圧ベント口のうち、少なくとも一つの減圧ベント口が、それよりも押出方向下流側にある減圧ベント口よりも、絶対圧力が低いような態様を含むものであればよく、その具体的な態様は特に限定されない。 As described above, according to the present invention, as the invention according to the first aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
As the extruder, one having a plurality of decompression vent ports was used.
It is possible to provide a method for producing acrylic rubber in which the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is made higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
According to the invention according to the first aspect of the present invention, the water content of the acrylic rubber can be appropriately reduced while suppressing the occurrence of vent-up.
In the invention according to the first aspect of the present invention, when there are three or more decompression vents, at least one of the three or more decompression vents is downstream in the extrusion direction. Any embodiment may include an aspect in which the absolute pressure is lower than that of the pressure reducing vent port on the side, and the specific embodiment thereof is not particularly limited.
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機として、減圧ベント口を複数有するものを用い、
押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高くする、アクリルゴムの製造方法を提供することができる。
本発明の第1の観点に係る発明によれば、ベントアップの発生を抑制しながら、アクリルゴムの含水率を適切に低減することができる。
なお、本発明の第1の観点に係る発明において、減圧ベント口が3個以上ある場合には、3個以上ある減圧ベント口のうち、少なくとも一つの減圧ベント口が、それよりも押出方向下流側にある減圧ベント口よりも、絶対圧力が低いような態様を含むものであればよく、その具体的な態様は特に限定されない。 As described above, according to the present invention, as the invention according to the first aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
As the extruder, one having a plurality of decompression vent ports was used.
It is possible to provide a method for producing acrylic rubber in which the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is made higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction.
According to the invention according to the first aspect of the present invention, the water content of the acrylic rubber can be appropriately reduced while suppressing the occurrence of vent-up.
In the invention according to the first aspect of the present invention, when there are three or more decompression vents, at least one of the three or more decompression vents is downstream in the extrusion direction. Any embodiment may include an aspect in which the absolute pressure is lower than that of the pressure reducing vent port on the side, and the specific embodiment thereof is not particularly limited.
また、本発明によれば、第2の観点に係る発明として、
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機として、覗き窓を有する減圧ベント口を備えるものを用いる、アクリルゴムの製造方法を提供することができる。
本発明の第2の観点に係る発明によれば、ベントアップの発生の有無を容易に確認することができる。 Further, according to the present invention, as an invention according to the second aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
A method for producing acrylic rubber can be provided, in which the extruder is provided with a pressure reducing vent port having a viewing window.
According to the invention according to the second aspect of the present invention, it is possible to easily confirm the presence or absence of the occurrence of vent-up.
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機として、覗き窓を有する減圧ベント口を備えるものを用いる、アクリルゴムの製造方法を提供することができる。
本発明の第2の観点に係る発明によれば、ベントアップの発生の有無を容易に確認することができる。 Further, according to the present invention, as an invention according to the second aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
A method for producing acrylic rubber can be provided, in which the extruder is provided with a pressure reducing vent port having a viewing window.
According to the invention according to the second aspect of the present invention, it is possible to easily confirm the presence or absence of the occurrence of vent-up.
また、本発明によれば、第3の観点に係る発明として、
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
アクリルゴムを、含水率60~70重量%であるクラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行う、アクリルゴムの製造方法が提供される。
本発明の第3の観点に係る発明によれば、最終的に得られる乾燥後のアクリルゴム中に含まれる凝固剤量を低く抑えることができるとともに、排水スリットからの、クラムのスリット抜けの発生を低減することができる。 Further, according to the present invention, as an invention according to the third aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
Provided is a method for producing acrylic rubber, in which acrylic rubber is put into the extruder in a crumb state having a water content of 60 to 70% by weight to dry the acrylic rubber.
According to the invention according to the third aspect of the present invention, the amount of the coagulant contained in the finally obtained dried acrylic rubber can be suppressed to a low level, and the clam slit is removed from the drainage slit. Can be reduced.
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
アクリルゴムを、含水率60~70重量%であるクラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行う、アクリルゴムの製造方法が提供される。
本発明の第3の観点に係る発明によれば、最終的に得られる乾燥後のアクリルゴム中に含まれる凝固剤量を低く抑えることができるとともに、排水スリットからの、クラムのスリット抜けの発生を低減することができる。 Further, according to the present invention, as an invention according to the third aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
Provided is a method for producing acrylic rubber, in which acrylic rubber is put into the extruder in a crumb state having a water content of 60 to 70% by weight to dry the acrylic rubber.
According to the invention according to the third aspect of the present invention, the amount of the coagulant contained in the finally obtained dried acrylic rubber can be suppressed to a low level, and the clam slit is removed from the drainage slit. Can be reduced.
また、本発明によれば、第4の観点に係る発明として、
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機で単位時間当たりに乾燥されるアクリルゴムの処理量をQ[kg/h]、前記スクリューの回転数をN[rpm]としたとき、下記式(1)を満たす、アクリルゴムの製造方法が提供される。
3≦Q/N≦8 (1)
本発明の第4の観点に係る発明によれば、含水率が適切に低減されたアクリルゴムを、高い生産性にて生産できるという効果を効果的に高めることができるものである。 Further, according to the present invention, as an invention according to the fourth aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
Production of acrylic rubber satisfying the following formula (1) when the processing amount of acrylic rubber dried by the extruder per unit time is Q [kg / h] and the rotation speed of the screw is N [rpm]. The method is provided.
3 ≦ Q / N ≦ 8 (1)
According to the invention according to the fourth aspect of the present invention, it is possible to effectively enhance the effect that acrylic rubber having an appropriately reduced water content can be produced with high productivity.
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機で単位時間当たりに乾燥されるアクリルゴムの処理量をQ[kg/h]、前記スクリューの回転数をN[rpm]としたとき、下記式(1)を満たす、アクリルゴムの製造方法が提供される。
3≦Q/N≦8 (1)
本発明の第4の観点に係る発明によれば、含水率が適切に低減されたアクリルゴムを、高い生産性にて生産できるという効果を効果的に高めることができるものである。 Further, according to the present invention, as an invention according to the fourth aspect,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
Production of acrylic rubber satisfying the following formula (1) when the processing amount of acrylic rubber dried by the extruder per unit time is Q [kg / h] and the rotation speed of the screw is N [rpm]. The method is provided.
3 ≦ Q / N ≦ 8 (1)
According to the invention according to the fourth aspect of the present invention, it is possible to effectively enhance the effect that acrylic rubber having an appropriately reduced water content can be produced with high productivity.
また、本発明によれば、第5の観点に係る発明として、
洗浄タンク内で、アクリルゴムを洗浄する洗浄工程と、
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程とを備え
前記洗浄工程と前記乾燥工程とを連続工程とする、アクリルゴムの製造方法が提供される。
本発明の第5の観点に係る発明によれば、省スペース化および生産効率の向上を可能とすることができ、さらには、製造安定性をも高めることもできる。 Further, according to the present invention, as an invention according to the fifth aspect,
A cleaning process that cleans acrylic rubber in the cleaning tank,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel, and the washing step and the drying step are continuous steps. Provided.
According to the invention according to the fifth aspect of the present invention, it is possible to save space and improve production efficiency, and further, it is possible to improve production stability.
洗浄タンク内で、アクリルゴムを洗浄する洗浄工程と、
バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程とを備え
前記洗浄工程と前記乾燥工程とを連続工程とする、アクリルゴムの製造方法が提供される。
本発明の第5の観点に係る発明によれば、省スペース化および生産効率の向上を可能とすることができ、さらには、製造安定性をも高めることもできる。 Further, according to the present invention, as an invention according to the fifth aspect,
A cleaning process that cleans acrylic rubber in the cleaning tank,
A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel, and the washing step and the drying step are continuous steps. Provided.
According to the invention according to the fifth aspect of the present invention, it is possible to save space and improve production efficiency, and further, it is possible to improve production stability.
以下に、実施例および比較例を挙げて、本発明についてより具体的に説明する。なお、各例中の「部」は、特に断りのない限り、重量基準である。
各種の物性については、以下の方法に従って評価した。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, "parts" in each example are based on weight.
Various physical properties were evaluated according to the following methods.
各種の物性については、以下の方法に従って評価した。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, "parts" in each example are based on weight.
Various physical properties were evaluated according to the following methods.
<合成例1>
温度計、攪拌装置、窒素導入管および減圧装置を備えた重合反応器に、水200部、ラウリル硫酸ナトリウム3部およびアクリル酸エチル15部、アクリル酸n-ブチル55部、アクリル酸メトキシエチル28部およびフマル酸モノn-ブチル2部を仕込んだ。その後、減圧による脱気および窒素置換をくり返して酸素を十分除去した後、ナトリウムホルムアルデヒドスルホキシレート0.002部およびクメンハイドロパーオキシド0.005部を加えて常圧、常温下で乳化重合反応を開始させ、重合転化率が95%に達するまで反応を継続することで、アクリルゴムのラテックスを得た。次いで、得られたアクリルゴムのラテックスを塩化カルシウム水溶液で凝固させることで、アクリルゴムのスラリー(固形分濃度32重量%)を得た。 <Synthesis example 1>
200 parts of water, 3 parts of sodium lauryl sulfate and 15 parts of ethyl acrylate, 55 parts of n-butyl acrylate, 28 parts of methoxyethyl acrylate in a polymerization reactor equipped with a thermometer, agitator, nitrogen introduction tube and decompression device. And 2 parts of mono-n-butyl fumarate were charged. After that, oxygen was sufficiently removed by repeating degassing and nitrogen substitution under reduced pressure, and then 0.002 parts of sodium formaldehyde sulfoxylate and 0.005 parts of cumene hydroperoxide were added to carry out an emulsion polymerization reaction at normal pressure and normal temperature. Acrylic rubber latex was obtained by starting and continuing the reaction until the polymerization conversion rate reached 95%. Next, the obtained latex of acrylic rubber was coagulated with an aqueous calcium chloride solution to obtain a slurry of acrylic rubber (solid content concentration: 32% by weight).
温度計、攪拌装置、窒素導入管および減圧装置を備えた重合反応器に、水200部、ラウリル硫酸ナトリウム3部およびアクリル酸エチル15部、アクリル酸n-ブチル55部、アクリル酸メトキシエチル28部およびフマル酸モノn-ブチル2部を仕込んだ。その後、減圧による脱気および窒素置換をくり返して酸素を十分除去した後、ナトリウムホルムアルデヒドスルホキシレート0.002部およびクメンハイドロパーオキシド0.005部を加えて常圧、常温下で乳化重合反応を開始させ、重合転化率が95%に達するまで反応を継続することで、アクリルゴムのラテックスを得た。次いで、得られたアクリルゴムのラテックスを塩化カルシウム水溶液で凝固させることで、アクリルゴムのスラリー(固形分濃度32重量%)を得た。 <Synthesis example 1>
200 parts of water, 3 parts of sodium lauryl sulfate and 15 parts of ethyl acrylate, 55 parts of n-butyl acrylate, 28 parts of methoxyethyl acrylate in a polymerization reactor equipped with a thermometer, agitator, nitrogen introduction tube and decompression device. And 2 parts of mono-n-butyl fumarate were charged. After that, oxygen was sufficiently removed by repeating degassing and nitrogen substitution under reduced pressure, and then 0.002 parts of sodium formaldehyde sulfoxylate and 0.005 parts of cumene hydroperoxide were added to carry out an emulsion polymerization reaction at normal pressure and normal temperature. Acrylic rubber latex was obtained by starting and continuing the reaction until the polymerization conversion rate reached 95%. Next, the obtained latex of acrylic rubber was coagulated with an aqueous calcium chloride solution to obtain a slurry of acrylic rubber (solid content concentration: 32% by weight).
<実施例1>
合成例1で得られたアクリルゴムのスラリーについて、図1に示す洗浄タンク7および押出機1を用いて、洗浄および乾燥を行うことで、固形状のアクリルゴムを得た。実施例1においては、洗浄タンク7において洗浄を行う際における、アクリルゴムの洗浄タンク7への供給レートを500kg/h(固形ゴム分換算での供給レート)、洗浄水の洗浄タンク7への供給レートを12000kg/hとして、洗浄を行った。また、洗浄後のアクリルゴムのスラリーは、洗浄タンク7から水除去設備8(スリット・スクリーン)を通して、アクリルゴムの含水クラム(含水率:60重量%)として(含水クラムに、水が同伴した態様であって、水の存在割合が60重量%である状態にて)、押出機1に、1250kg/hの供給レート(アクリルゴム換算での供給レート(すなわち、乾燥されるアクリルゴムの処理量Q)は、500kg/h)にて供給して、押出機1による乾燥を行った。また、押出機1に投入する際における、アクリルゴムの含水クラムの温度は40℃とした。 <Example 1>
The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using thewashing tank 7 and the extruder 1 shown in FIG. 1 to obtain a solid acrylic rubber. In the first embodiment, the supply rate of acrylic rubber to the cleaning tank 7 when cleaning in the cleaning tank 7 is 500 kg / h (supply rate in terms of solid rubber content), and the cleaning water is supplied to the cleaning tank 7. Washing was performed at a rate of 12000 kg / h. Further, the acrylic rubber slurry after cleaning is passed through the water removal facility 8 (slit screen) from the cleaning tank 7 as a water content crumb (moisture content: 60% by weight) of the acrylic rubber (a mode in which water is accompanied by the water content crumb). (In a state where the water content is 60% by weight), the supply rate of 1250 kg / h to the extruder 1 (supply rate in terms of acrylic rubber (that is, the amount of acrylic rubber to be dried Q). ) Was supplied at 500 kg / h) and dried by the extruder 1. Further, the temperature of the water-containing crumb of acrylic rubber at the time of charging into the extruder 1 was set to 40 ° C.
合成例1で得られたアクリルゴムのスラリーについて、図1に示す洗浄タンク7および押出機1を用いて、洗浄および乾燥を行うことで、固形状のアクリルゴムを得た。実施例1においては、洗浄タンク7において洗浄を行う際における、アクリルゴムの洗浄タンク7への供給レートを500kg/h(固形ゴム分換算での供給レート)、洗浄水の洗浄タンク7への供給レートを12000kg/hとして、洗浄を行った。また、洗浄後のアクリルゴムのスラリーは、洗浄タンク7から水除去設備8(スリット・スクリーン)を通して、アクリルゴムの含水クラム(含水率:60重量%)として(含水クラムに、水が同伴した態様であって、水の存在割合が60重量%である状態にて)、押出機1に、1250kg/hの供給レート(アクリルゴム換算での供給レート(すなわち、乾燥されるアクリルゴムの処理量Q)は、500kg/h)にて供給して、押出機1による乾燥を行った。また、押出機1に投入する際における、アクリルゴムの含水クラムの温度は40℃とした。 <Example 1>
The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using the
押出機1による乾燥の条件としては、供給ゾーン100のバレル温度:80℃、脱水ゾーン102のバレル温度:130℃、および乾燥ゾーン104のバレル温度:160℃とし、第1減圧ベント口360の絶対圧力:90.3kPa、第2減圧ベント口380の絶対圧力:31.3kPa、第3減圧ベント口390の絶対圧力:4kPa、および第4減圧ベント口400の絶対圧力:4kPaとし(第1減圧ベント口360の絶対圧力と、第4減圧ベント口400の絶対圧力との差が、86.3kPa)、スクリュー6の回転数Nを100rpm(Q/N=5)とした。なお、実施例1においては、脱水ゾーン102を経た後の含水クラムの含水率は40重量%であった。
The conditions for drying by the extruder 1 are the barrel temperature of the supply zone 100: 80 ° C., the barrel temperature of the dehydration zone 102: 130 ° C., and the barrel temperature of the drying zone 104: 160 ° C., and the absolute pressure reducing vent port 360 of the first decompression vent port 360. Pressure: 90.3 kPa, absolute pressure of the second decompression vent port 380: 31.3 kPa, absolute pressure of the third decompression vent port 390: 4 kPa, and absolute pressure of the fourth decompression vent port 400: 4 kPa (first decompression vent). The difference between the absolute pressure of the port 360 and the absolute pressure of the fourth decompression vent port 400 was 86.3 kPa), and the rotation speed N of the screw 6 was set to 100 rpm (Q / N = 5). In Example 1, the water content of the water-containing crumb after passing through the dehydration zone 102 was 40% by weight.
実施例1によれば、洗浄タンク7および押出機1により、アクリルゴムのスラリーの洗浄、およびアクリルゴムの含水クラムの乾燥を行い、固形状のアクリルゴムを連続的に得るという操作を2時間連続して行った結果、各減圧ベント口のベントアップは、発生せず、また、得られた固形状のアクリルゴムも含水率が0.7重量%と低減されたものであった。なお、得られた固形状のアクリルゴムのムーニー粘度(ML1+4、100℃)(JIS K6300-1に従って測定。以下、同様。)は、32であった。
According to the first embodiment, the washing tank 7 and the extruder 1 are used to wash the acrylic rubber slurry and dry the water-containing crumb of the acrylic rubber to continuously obtain a solid acrylic rubber for 2 hours continuously. As a result, vent-up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.7% by weight. The Mooney viscosity (ML1 + 4, 100 ° C.) (measured according to JIS K6300-1; the same applies hereinafter) of the obtained solid acrylic rubber was 32.
<実施例2>
押出機1により乾燥を行う際における各減圧ベント口の絶対圧力を、第1減圧ベント口360の絶対圧力:41.3kPa、第2減圧ベント口380の絶対圧力:41.3kPa、第3減圧ベント口390の絶対圧力:36.3kPa、および第4減圧ベント口400の絶対圧力:31.3kPaとした(第1減圧ベント口360の絶対圧力と、第4減圧ベント口400の絶対圧力との差が、10kPa)以外は、実施例1と同様にして、アクリルゴムのスラリーの洗浄、およびアクリルゴムの含水クラムの乾燥を行い、固形状のアクリルゴムを連続的に得るという操作を2時間連続して行った。なお、実施例2においては、脱水ゾーン102を経た後の含水クラムの含水率は40重量%であった。その結果、実施例2においても、各減圧ベント口のベントアップは、発生せず、また、得られた固形状のアクリルゴムも含水率が0.2重量%と低減されたものであった。なお、得られた固形状のアクリルゴムのムーニー粘度(ML1+4、100℃)は、34であった。 <Example 2>
The absolute pressure of each decompression vent port when drying by theextruder 1 is as follows: absolute pressure of the first decompression vent port 360: 41.3 kPa, absolute pressure of the second decompression vent port 380: 41.3 kPa, third decompression vent. The absolute pressure of the port 390 was 36.3 kPa, and the absolute pressure of the fourth decompression vent port 400 was 31.3 kPa (the difference between the absolute pressure of the first decompression vent port 360 and the absolute pressure of the fourth decompression vent port 400). However, except for 10 kPa), the operation of washing the acrylic rubber slurry and drying the acrylic rubber-containing crumb to continuously obtain solid acrylic rubber was continuously performed for 2 hours in the same manner as in Example 1. I went. In Example 2, the water content of the water-containing crumb after passing through the dehydration zone 102 was 40% by weight. As a result, also in Example 2, vent-up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.2% by weight. The Mooney viscosity (ML1 + 4, 100 ° C.) of the obtained solid acrylic rubber was 34.
押出機1により乾燥を行う際における各減圧ベント口の絶対圧力を、第1減圧ベント口360の絶対圧力:41.3kPa、第2減圧ベント口380の絶対圧力:41.3kPa、第3減圧ベント口390の絶対圧力:36.3kPa、および第4減圧ベント口400の絶対圧力:31.3kPaとした(第1減圧ベント口360の絶対圧力と、第4減圧ベント口400の絶対圧力との差が、10kPa)以外は、実施例1と同様にして、アクリルゴムのスラリーの洗浄、およびアクリルゴムの含水クラムの乾燥を行い、固形状のアクリルゴムを連続的に得るという操作を2時間連続して行った。なお、実施例2においては、脱水ゾーン102を経た後の含水クラムの含水率は40重量%であった。その結果、実施例2においても、各減圧ベント口のベントアップは、発生せず、また、得られた固形状のアクリルゴムも含水率が0.2重量%と低減されたものであった。なお、得られた固形状のアクリルゴムのムーニー粘度(ML1+4、100℃)は、34であった。 <Example 2>
The absolute pressure of each decompression vent port when drying by the
<実施例3>
合成例1で得られたアクリルゴムのスラリーについて、図1に示す洗浄タンク7および押出機1を用いて、洗浄および乾燥を行うことで、固形状のアクリルゴムを得た。実施例3においては、洗浄タンク7において洗浄を行う際における、アクリルゴムの洗浄タンク7への供給レートを400kg/h(固形ゴム分換算での供給レート)、洗浄水の洗浄タンク7への供給レートを9600kg/hとして、洗浄を行った。また、洗浄後のアクリルゴムのスラリーは、洗浄タンク7から水除去設備8(スリット・スクリーン)を通して、アクリルゴムの含水クラム(含水率:60重量%)として(含水クラムに、水が同伴した態様であって、水の存在割合が60重量%である状態にて)、押出機1に、1000kg/hの供給レート(アクリルゴム換算での供給レート(すなわち、乾燥されるアクリルゴムの処理量Q)は、400kg/h)にて供給して、押出機1による乾燥を行った。また、押出機1に投入する際における、アクリルゴムの含水クラムの温度は40℃とした。 <Example 3>
The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using thewashing tank 7 and the extruder 1 shown in FIG. 1 to obtain a solid acrylic rubber. In Example 3, when cleaning in the cleaning tank 7, the supply rate of acrylic rubber to the cleaning tank 7 is 400 kg / h (supply rate in terms of solid rubber content), and the cleaning water is supplied to the cleaning tank 7. Washing was performed at a rate of 9600 kg / h. Further, the acrylic rubber slurry after cleaning is passed through the water removal facility 8 (slit screen) from the cleaning tank 7 as a water content crumb (moisture content: 60% by weight) of the acrylic rubber (a mode in which water is accompanied by the water content crumb). In the state where the water content is 60% by weight, the extruder 1 is supplied with a supply rate of 1000 kg / h (supply rate in terms of acrylic rubber (that is, the amount of acrylic rubber to be dried Q). ) Was supplied at 400 kg / h) and dried by the extruder 1. Further, the temperature of the water-containing crumb of acrylic rubber at the time of charging into the extruder 1 was set to 40 ° C.
合成例1で得られたアクリルゴムのスラリーについて、図1に示す洗浄タンク7および押出機1を用いて、洗浄および乾燥を行うことで、固形状のアクリルゴムを得た。実施例3においては、洗浄タンク7において洗浄を行う際における、アクリルゴムの洗浄タンク7への供給レートを400kg/h(固形ゴム分換算での供給レート)、洗浄水の洗浄タンク7への供給レートを9600kg/hとして、洗浄を行った。また、洗浄後のアクリルゴムのスラリーは、洗浄タンク7から水除去設備8(スリット・スクリーン)を通して、アクリルゴムの含水クラム(含水率:60重量%)として(含水クラムに、水が同伴した態様であって、水の存在割合が60重量%である状態にて)、押出機1に、1000kg/hの供給レート(アクリルゴム換算での供給レート(すなわち、乾燥されるアクリルゴムの処理量Q)は、400kg/h)にて供給して、押出機1による乾燥を行った。また、押出機1に投入する際における、アクリルゴムの含水クラムの温度は40℃とした。 <Example 3>
The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using the
押出機1による乾燥の条件としては、供給ゾーン100のバレル温度:80℃、脱水ゾーン102のバレル温度:130℃、および乾燥ゾーン104のバレル温度:160℃とし、第1減圧ベント口360の絶対圧力:41kPa、第2減圧ベント口380の絶対圧力:41kPa、第3減圧ベント口390の絶対圧力:30kPa、および第4減圧ベント口400の絶対圧力:25kPaとし(第1減圧ベント口360の絶対圧力と、第4減圧ベント口400の絶対圧力との差が、16kPa)、スクリュー6の回転数Nを100rpm(Q/N=4)とした。なお、実施例3においては、脱水ゾーン102を経た後の含水クラムの含水率は20重量%であった。
The conditions for drying by the extruder 1 are the barrel temperature of the supply zone 100: 80 ° C., the barrel temperature of the dehydration zone 102: 130 ° C., and the barrel temperature of the drying zone 104: 160 ° C., and the absolute decompression vent port 360 Pressure: 41 kPa, absolute pressure of the second decompression vent port 380: 41 kPa, absolute pressure of the third decompression vent port 390: 30 kPa, and absolute pressure of the fourth decompression vent port 400: 25 kPa (absolute of the first decompression vent port 360). The difference between the pressure and the absolute pressure of the fourth decompression vent port 400 was 16 kPa), and the rotation speed N of the screw 6 was set to 100 rpm (Q / N = 4). In Example 3, the water content of the water-containing crumb after passing through the dehydration zone 102 was 20% by weight.
実施例3によれば、洗浄タンク7および押出機1により、アクリルゴムのスラリーの洗浄、およびアクリルゴムの含水クラムの乾燥を行い、固形状のアクリルゴムを連続的に得るという操作を2時間連続して行った結果、各減圧ベント口のベントアップは、発生せず、また、得られた固形状のアクリルゴムも含水率が0.4重量%と低減されたものであった。なお、得られた固形状のアクリルゴムのムーニー粘度(ML1+4、100℃)は、32であった。
According to the third embodiment, the washing tank 7 and the extruder 1 wash the acrylic rubber slurry and dry the water-containing crumb of the acrylic rubber to continuously obtain solid acrylic rubber for two hours continuously. As a result, venting up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.4% by weight. The Mooney viscosity (ML1 + 4, 100 ° C.) of the obtained solid acrylic rubber was 32.
<実施例4>
合成例1で得られたアクリルゴムのスラリーについて、図1に示す洗浄タンク7および押出機1を用いて、洗浄および乾燥を行うことで、固形状のアクリルゴムを得た。実施例4においては、洗浄タンク7において洗浄を行う際における、アクリルゴムの洗浄タンク7への供給レートを500kg/h(固形ゴム分換算での供給レート)、洗浄水の洗浄タンク7への供給レートを12000kg/hとして、洗浄を行った。また、洗浄後のアクリルゴムのスラリーは、洗浄タンク7から水除去設備8(スリット・スクリーン)を通して、アクリルゴムの含水クラム(含水率:60重量%)として(含水クラムに、水が同伴した態様であって、水の存在割合が60重量%である状態にて)、押出機1に、1250kg/hの供給レート(アクリルゴム換算での供給レート(すなわち、乾燥されるアクリルゴムの処理量Q)は、500kg/h)にて供給して、押出機1による乾燥を行った。また、押出機1に投入する際における、アクリルゴムの含水クラムの温度は65℃とした。なお、押出機1に投入する際における、アクリルゴムの含水クラムの温度は、洗浄タンク7における洗浄を行う際の洗浄水の温度を調整することにより行った。 <Example 4>
The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using thewashing tank 7 and the extruder 1 shown in FIG. 1 to obtain a solid acrylic rubber. In the fourth embodiment, the supply rate of acrylic rubber to the cleaning tank 7 when cleaning is performed in the cleaning tank 7 is 500 kg / h (supply rate in terms of solid rubber content), and the cleaning water is supplied to the cleaning tank 7. Washing was performed at a rate of 12000 kg / h. Further, the acrylic rubber slurry after cleaning is passed through the water removal facility 8 (slit screen) from the cleaning tank 7 as a water content crumb (moisture content: 60% by weight) of the acrylic rubber (a mode in which water is accompanied by the water content crumb). (In a state where the water content is 60% by weight), the supply rate of 1250 kg / h to the extruder 1 (supply rate in terms of acrylic rubber (that is, the amount of acrylic rubber to be dried Q). ) Was supplied at 500 kg / h) and dried by the extruder 1. Further, the temperature of the water-containing crumb of acrylic rubber at the time of charging into the extruder 1 was set to 65 ° C. The temperature of the water-containing crumb of acrylic rubber when it was put into the extruder 1 was adjusted by adjusting the temperature of the washing water when washing in the washing tank 7.
合成例1で得られたアクリルゴムのスラリーについて、図1に示す洗浄タンク7および押出機1を用いて、洗浄および乾燥を行うことで、固形状のアクリルゴムを得た。実施例4においては、洗浄タンク7において洗浄を行う際における、アクリルゴムの洗浄タンク7への供給レートを500kg/h(固形ゴム分換算での供給レート)、洗浄水の洗浄タンク7への供給レートを12000kg/hとして、洗浄を行った。また、洗浄後のアクリルゴムのスラリーは、洗浄タンク7から水除去設備8(スリット・スクリーン)を通して、アクリルゴムの含水クラム(含水率:60重量%)として(含水クラムに、水が同伴した態様であって、水の存在割合が60重量%である状態にて)、押出機1に、1250kg/hの供給レート(アクリルゴム換算での供給レート(すなわち、乾燥されるアクリルゴムの処理量Q)は、500kg/h)にて供給して、押出機1による乾燥を行った。また、押出機1に投入する際における、アクリルゴムの含水クラムの温度は65℃とした。なお、押出機1に投入する際における、アクリルゴムの含水クラムの温度は、洗浄タンク7における洗浄を行う際の洗浄水の温度を調整することにより行った。 <Example 4>
The acrylic rubber slurry obtained in Synthesis Example 1 was washed and dried using the
押出機1による乾燥の条件としては、供給ゾーン100のバレル温度:90℃、脱水ゾーン102のバレル温度:140℃、および乾燥ゾーン104のバレル温度:170℃とし、第1減圧ベント口360の絶対圧力:65kPa、第2減圧ベント口380の絶対圧力:55kPa、第3減圧ベント口390の絶対圧力:40kPa、および第4減圧ベント口400の絶対圧力:35kPaとし(第1減圧ベント口360の絶対圧力と、第4減圧ベント口400の絶対圧力との差が、30kPa)、スクリュー6の回転数Nを100rpm(Q/N=5)とした。なお、実施例3においては、脱水ゾーン102を経た後の含水クラムの含水率は40重量%であった。
The conditions for drying by the extruder 1 are the barrel temperature of the supply zone 100: 90 ° C., the barrel temperature of the dehydration zone 102: 140 ° C., and the barrel temperature of the drying zone 104: 170 ° C., and the absolute decompression vent port 360 Pressure: 65 kPa, absolute pressure of the second decompression vent port 380: 55 kPa, absolute pressure of the third decompression vent port 390: 40 kPa, and absolute pressure of the fourth decompression vent port 400: 35 kPa (absolute of the first decompression vent port 360). The difference between the pressure and the absolute pressure of the fourth decompression vent port 400 was 30 kPa), and the rotation speed N of the screw 6 was 100 rpm (Q / N = 5). In Example 3, the water content of the water-containing crumb after passing through the dehydration zone 102 was 40% by weight.
実施例3によれば、洗浄タンク7および押出機1により、アクリルゴムのスラリーの洗浄、およびアクリルゴムの含水クラムの乾燥を行い、固形状のアクリルゴムを連続的に得るという操作を2時間連続して行った結果、各減圧ベント口のベントアップは、発生せず、また、得られた固形状のアクリルゴムも含水率が0.4重量%と低減されたものであった。なお、得られた固形状のアクリルゴムのムーニー粘度(ML1+4、100℃)は、32であった。
According to the third embodiment, the washing tank 7 and the extruder 1 wash the acrylic rubber slurry and dry the water-containing crumb of the acrylic rubber to continuously obtain a solid acrylic rubber for 2 hours continuously. As a result, venting up of each decompression vent port did not occur, and the obtained solid acrylic rubber also had a water content reduced to 0.4% by weight. The Mooney viscosity (ML1 + 4, 100 ° C.) of the obtained solid acrylic rubber was 32.
<比較例1>
押出機1により乾燥を行う際における各減圧ベント口の圧力を、第1減圧ベント口360の絶対圧力:4kPa、第2減圧ベント口380の絶対圧力:4kPa、第3減圧ベント口390の絶対圧力:4kPa、および第4減圧ベント口400の絶対圧力:4kPaとした(第1減圧ベント口360の絶対圧力と、第4減圧ベント口400の絶対圧力とが同じ)以外は、実施例1と同様にして、アクリルゴムのスラリーの洗浄、およびアクリルゴムの含水クラムの乾燥を行い、固形状のアクリルゴムを連続的に得るという操作を30分連続して行った。なお、比較例1においては、脱水ゾーン102を経た後の含水クラムの含水率は40重量%であった。その結果、比較例1においては、第1減圧ベント口360および第2減圧ベント口380において、ベントアップが発生してしまう結果となった。 <Comparative example 1>
The pressure of eachdecompression vent port 360 when drying is performed by the extruder 1, the absolute pressure of the first decompression vent port 360: 4 kPa, the absolute pressure of the second decompression vent port 380: 4 kPa, the absolute pressure of the third decompression vent port 390. The same as in Example 1 except that the absolute pressure of the 4th decompression vent port 400 was 4 kPa and the absolute pressure of the 4th decompression vent port 400 was 4 kPa (the absolute pressure of the 1st decompression vent port 360 and the absolute pressure of the 4th decompression vent port 400 are the same). Then, the slurry of the acrylic rubber was washed and the water-containing crumb of the acrylic rubber was dried, and the solid acrylic rubber was continuously obtained for 30 minutes. In Comparative Example 1, the water content of the water-containing crumb after passing through the dehydration zone 102 was 40% by weight. As a result, in Comparative Example 1, venting occurred at the first decompression vent port 360 and the second decompression vent port 380.
押出機1により乾燥を行う際における各減圧ベント口の圧力を、第1減圧ベント口360の絶対圧力:4kPa、第2減圧ベント口380の絶対圧力:4kPa、第3減圧ベント口390の絶対圧力:4kPa、および第4減圧ベント口400の絶対圧力:4kPaとした(第1減圧ベント口360の絶対圧力と、第4減圧ベント口400の絶対圧力とが同じ)以外は、実施例1と同様にして、アクリルゴムのスラリーの洗浄、およびアクリルゴムの含水クラムの乾燥を行い、固形状のアクリルゴムを連続的に得るという操作を30分連続して行った。なお、比較例1においては、脱水ゾーン102を経た後の含水クラムの含水率は40重量%であった。その結果、比較例1においては、第1減圧ベント口360および第2減圧ベント口380において、ベントアップが発生してしまう結果となった。 <Comparative example 1>
The pressure of each
1… 押出機
2… 駆動ユニット
3… バレル
31~41… バレルブロック
360… 第1減圧ベント口
380… 第2減圧ベント口
390… 第3減圧ベント口
400… 第4減圧ベント口
361,381,391,401… 覗き窓
5… ダイ
6… スクリュー
7… 洗浄タンク
8… 水除去設備 1 ...Extruder 2 ... Drive unit 3 ... Barrels 31-41 ... Barrel block 360 ... 1st decompression vent port 380 ... 2nd decompression vent port 390 ... 3rd decompression vent port 400 ... 4th decompression vent port 361,381,391 , 401 ... Peep window 5 ... Die 6 ... Screw 7 ... Cleaning tank 8 ... Water removal equipment
2… 駆動ユニット
3… バレル
31~41… バレルブロック
360… 第1減圧ベント口
380… 第2減圧ベント口
390… 第3減圧ベント口
400… 第4減圧ベント口
361,381,391,401… 覗き窓
5… ダイ
6… スクリュー
7… 洗浄タンク
8… 水除去設備 1 ...
Claims (9)
- バレルの内部にスクリューが回転駆動自在に配置されている押出機を用いて、アクリルゴムを乾燥する乾燥工程を備える、アクリルゴムの製造方法であって、
前記押出機として、減圧ベント口を複数有するものを用い、
押出方向上流側の減圧ベント口の絶対圧力を、押出方向下流側の減圧ベント口の絶対圧力よりも高くする、アクリルゴムの製造方法。 A method for producing acrylic rubber, which comprises a drying step of drying acrylic rubber using an extruder in which a screw is rotatably arranged inside a barrel.
As the extruder, one having a plurality of decompression vent ports was used.
A method for producing acrylic rubber, in which the absolute pressure of the decompression vent port on the upstream side in the extrusion direction is made higher than the absolute pressure of the decompression vent port on the downstream side in the extrusion direction. - 押出方向上流側の減圧ベント口の絶対圧力と、押出方向下流側の減圧ベント口の絶対圧力との差を、5.0~94.0kPaの範囲とする、請求項1に記載のアクリルゴムの製造方法。 The acrylic rubber according to claim 1, wherein the difference between the absolute pressure of the decompression vent port on the upstream side in the extrusion direction and the absolute pressure of the decompression vent port on the downstream side in the extrusion direction is in the range of 5.0 to 94.0 kPa. Production method.
- 前記押出機として、前記減圧ベント口を2つ以上有するものを用い、
2つ以上の前記減圧ベント口のうち、少なくとも2つの減圧ベント口の絶対圧力を、押出方向上流側から押出方向下流側に向かって、順に低くなるように設定する、請求項1または2に記載のアクリルゴムの製造方法。 As the extruder, one having two or more of the pressure reducing vent ports is used.
The first or second aspect of the present invention, wherein the absolute pressures of at least two of the two or more decompression vents are set to be lower in order from the upstream side in the extrusion direction to the downstream side in the extrusion direction. Acrylic rubber manufacturing method. - 前記押出機として、複数の前記減圧ベント口に、覗き窓を有するものを用いる、請求項1~3のいずれかに記載のアクリルゴムの製造方法。 The method for producing acrylic rubber according to any one of claims 1 to 3, wherein the extruder having a plurality of viewing windows at the decompression vent ports is used.
- アクリルゴムを、含水クラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行う請求項1~4のいずれかに記載のアクリルゴムの製造方法。 The method for producing acrylic rubber according to any one of claims 1 to 4, wherein the acrylic rubber is put into the extruder in a hydrous crumb state to dry the acrylic rubber.
- アクリルゴムを、含水率60~70重量%であるクラムの状態で、前記押出機に投入して、アクリルゴムの乾燥を行う請求項1~5のいずれかに記載のアクリルゴムの製造方法。 The method for producing acrylic rubber according to any one of claims 1 to 5, wherein the acrylic rubber is put into the extruder in a crumb state having a water content of 60 to 70% by weight to dry the acrylic rubber.
- 前記押出機として、複数の前記減圧ベント口よりも押出方向上流側に、押出方向上流側から順に、第1排出スリットおよび第2排出スリットを備えるものを用いる、請求項1~6のいずれかに記載のアクリルゴムの製造方法。 One of claims 1 to 6, wherein the extruder is provided with a first discharge slit and a second discharge slit in order from the upstream side in the extrusion direction on the upstream side in the extrusion direction from the plurality of pressure reducing vent ports. The method for manufacturing acrylic rubber described.
- 前記押出機で単位時間当たりに乾燥されるアクリルゴムの処理量をQ[kg/h]、前記スクリューの回転数をN[rpm]としたとき、下記式(1)を満たす、請求項1~7のいずれかに記載のアクリルゴムの製造方法。
3≦Q/N≦8 (1) Claims 1 to 1, wherein the following formula (1) is satisfied when the processing amount of acrylic rubber dried by the extruder per unit time is Q [kg / h] and the rotation speed of the screw is N [rpm]. 7. The method for producing acrylic rubber according to any one of 7.
3 ≦ Q / N ≦ 8 (1) - 洗浄タンク内で、アクリルゴムを洗浄する洗浄工程をさらに備え、
前記洗浄工程と前記乾燥工程とを、この順に連続工程とする請求項1~8のいずれかに記載のアクリルゴムの製造方法。 Further equipped with a cleaning process to clean the acrylic rubber in the cleaning tank,
The method for producing acrylic rubber according to any one of claims 1 to 8, wherein the cleaning step and the drying step are continuous steps in this order.
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