WO2017188400A1 - 共重合体の製造方法 - Google Patents
共重合体の製造方法 Download PDFInfo
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- WO2017188400A1 WO2017188400A1 PCT/JP2017/016824 JP2017016824W WO2017188400A1 WO 2017188400 A1 WO2017188400 A1 WO 2017188400A1 JP 2017016824 W JP2017016824 W JP 2017016824W WO 2017188400 A1 WO2017188400 A1 WO 2017188400A1
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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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
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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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
- C08F216/1433—Monomers containing side chains of polyethylene oxide groups
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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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Definitions
- the present invention relates to a method for producing a copolymer.
- the polymerization water is generally introduced into the polymerization kettle through a transfer pipe.
- polymerization water industrial water, pure water (water in which impurities are reduced by treatment such as deionization treatment, distillation treatment, reverse osmosis membrane treatment) and the like are generally used.
- pure water water in which impurities are reduced by treatment such as deionization treatment, distillation treatment, reverse osmosis membrane treatment
- polymerization water with less impurities is prepared by a pure water production process (see, for example, Patent Document 1).
- the polymerization reproducibility may be high or the polymerization reproducibility may be low, depending on the type of polymer or copolymer to be produced. It may interfere with the production of the product (copolymer).
- the present inventor in the production of a specific copolymer essentially comprising a structural unit derived from an unsaturated polyalkylene glycol ether monomer and a structural unit derived from an unsaturated monocarboxylic acid monomer, thus, even if the same pure water is used, depending on the type of polymer or copolymer to be produced, the polymerization reproducibility may be high or the polymerization reproducibility may be low. It was experienced during plant operation in an actual manufacturing plant that it was easy to interfere with the production of coalescence. For example, it has been found that when these copolymers are used in cement dispersant applications, the reproducibility of polymerization adversely affects cement dispersion performance. The means for solving such a problem was examined.
- the problem of the present invention is that in the production of a specific copolymer essentially comprising a structural unit derived from an unsaturated polyalkylene glycol ether monomer and a structural unit derived from an unsaturated monocarboxylic acid monomer.
- the method for producing the copolymer of the present invention comprises: 50% to 99% by weight of the structural unit (I) derived from the unsaturated polyalkylene glycol ether monomer (a) represented by the general formula (1), and the unsaturated monovalent represented by the general formula (2) 1% by weight to 50% by weight of the structural unit (II) derived from the carboxylic acid monomer (b), and a monomer copolymerizable with the monomer (a) and / or the monomer (b) (C) structural unit (III) derived from 0% to 49% by weight (provided that the total of structural unit (I), structural unit (II), and structural unit (III) is 100% by weight)
- a method for producing a copolymer comprising: A pure water production process for producing pure water having an electrical conductivity of 0.1 ⁇ S / cm to 100 ⁇ S / cm, and the pure water in a reaction kettle for producing the copolymer is passivated in resin or water.
- the conductivity of the pure water at a location where the pure water is introduced from the transfer pipe to the reaction kettle side is within a range of 0.1 ⁇ S / cm to 100 ⁇ S / cm. It is characterized by.
- Y 1 represents CH 2 ⁇ CR 0 — (CH 2 ) m —
- R 0 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- m is an integer of 0 to 2
- R 1 O represents one or more of oxyalkylene groups having 2 to 18 carbon atoms
- n is the average number of moles of oxyalkylene groups added and is greater than 0 and less than or equal to 500
- R 2 is Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
- R 3 , R 4 , and R 5 are the same or different and are a hydrogen atom or a methyl group, and M represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group.
- the material is a resin including at least one selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester, and Teflon (registered trademark), or chromium, aluminum, and titanium. It is at least one selected from alloys containing at least one selected from the group.
- the length L (m) of the transfer pipe, the flow rate V (m / sec) of pure water, and the inner radius R (m) of the transfer pipe are 1 0.0 ⁇ 10 2 seconds / m 2 ⁇ (L / V) / (2 ⁇ ⁇ R) ⁇ 3.0 ⁇ 10 5 seconds / m 2
- R 0 constituting Y 1 in the general formula (1) is a hydrogen atom or a methyl group.
- the unsaturated monocarboxylic acid monomer (b) is a (meth) acrylic acid monomer.
- the ratio of the unsaturated polyalkylene glycol ether monomer (a) to the unsaturated monocarboxylic acid monomer (b) is expressed as follows: ⁇ the monomer ( b) / (the monomer (a) + the monomer (b)) ⁇ ⁇ 100 ⁇ 5.8.
- the copolymer has a weight average molecular weight of 10,000 to 300,000 in terms of polyethylene glycol by gel permeation chromatography.
- the weight average molecular weight of the obtained copolymer is 10,000 to 300,000 in terms of polyethylene glycol by gel permeation chromatography.
- the coefficient of variation CV of the weight average molecular weight of the obtained copolymer is 0.04 or less.
- a copolymer has a weight average molecular weight of 10,000 to 300,000 in terms of polyethylene glycol by gel permeation chromatography, a coefficient of variation CV of the weight average molecular weight of 0.04 or less, and the general formula (1) 50% to 99% by weight of the structural unit (I) derived from the unsaturated polyalkylene glycol ether monomer (a) represented by formula (2), and an unsaturated monocarboxylic acid based monomer represented by the general formula (2) Derived from 1% by weight to 50% by weight of the structural unit (II) derived from the body (b) and the monomer (a) and / or the monomer (c) copolymerizable with the monomer (b)
- the structural unit (III) is 0 to 49% by weight (provided that the total of the structural unit (I), the structural unit (II), and the structural unit (III) is 100% by weight).
- Y 1 represents CH 2 ⁇ CR 0 — (CH 2 ) m —
- R 0 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- m is an integer of 0 to 2
- R 1 O represents one or more of oxyalkylene groups having 2 to 18 carbon atoms
- n is the average number of moles of oxyalkylene groups added and is greater than 0 and less than or equal to 500
- R 2 is Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
- R 3 , R 4 , and R 5 are the same or different and are a hydrogen atom or a methyl group
- M represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group.
- the expression “(meth) acryl” means “acryl and / or methacryl”, and the expression “(meth) acrylate” means “acrylate and / or methacrylate”.
- the expression “acid (salt)” means “acid and / or salt thereof”.
- mass when there is an expression “mass” in the present specification, it may be read as “weight” conventionally used as a unit of weight in general, and conversely, “weight” in the present specification. May be read as “mass”, which is commonly used as an SI system unit indicating weight.
- the unsaturated carboxylic acid monomer (b) is in the form of a salt (ie, carboxylate) Is calculated assuming that the salt form is not taken.
- a salt ie, carboxylate
- the salt form is not taken.
- sodium acrylate it is calculated as acrylic acid.
- the method for producing a copolymer of the present invention is a method for producing a specific copolymer (described in detail later), and includes a pure water production step, a pure water transfer step, and a polymerization step.
- a pure water storage step may be included between the pure water production step and the pure water transfer step.
- pure water having a conductivity of 0.1 ⁇ S / cm to 100 ⁇ S / cm is produced.
- the “pure water” referred to in this specification is water obtained by reducing impurities by performing treatments such as deionization treatment, distillation treatment, and reverse osmosis membrane treatment on industrial water and tap water.
- the conductivity is a value measured at a water temperature of 25 ° C.
- any appropriate process can be adopted as long as it is a process capable of producing pure water having an electrical conductivity of 0.1 ⁇ S / cm to 100 ⁇ S / cm.
- a pure water production process introduced in various production plants can be employed.
- the conductivity of pure water produced in the pure water production process is 0.1 ⁇ S / cm to 100 ⁇ S / cm, preferably 0.1 ⁇ S / cm to 80 ⁇ S / cm, more preferably 0.1 ⁇ S / cm to It is 60 ⁇ S / cm, more preferably 0.1 ⁇ S / cm to 40 ⁇ S / cm, and particularly preferably 0.1 ⁇ S / cm to 20 ⁇ S / cm.
- the pure water produced in the pure water production process is transferred to the reaction kettle in which the polymerization process is performed.
- transfer is performed by transfer piping. That is, pure water produced in the pure water production process moves through the transfer pipe.
- the material of the transfer pipe is a resin or a substance that forms a passive state in water, preferably at least one selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyester, and Teflon (registered trademark). Or at least one selected from an alloy containing at least one selected from the group consisting of chromium, aluminum and titanium, and more preferably stainless steel (austenitic stainless steel, austenitic / ferritic stainless steel) Steel, ferritic stainless steel, martensitic stainless steel), and more preferably austenitic stainless steel such as SUS304 and SUS316.
- Passivation is a stable oxide film formed on the metal surface, and the generation of passivation suppresses corrosion of the transfer pipe and elution of metal components.
- the reason why it is necessary to use a specific material for the transfer pipe in this way is considered to be because a trace amount of impurities eluted from the transfer pipe also inhibits the production stability of the specific polymer.
- One of the achievements of the present invention is that the transfer pipe has a great influence on the mixing of trace impurities, and the influence can be suppressed.
- the length of the transfer pipe is preferably 1 m to 500 m, more preferably 1 m to 300 m, and further preferably 1 m to 200 m.
- the inner diameter of the transfer pipe is preferably 10 mm to 100 mm, more preferably 13 mm to 100 mm, and still more preferably 15 mm to 100 mm.
- the flow rate during transfer is preferably 0.1 m / sec to 10 m / sec, more preferably 0.2 m / sec to 10 m / sec, and further preferably 0.4 m / sec to 10 m / sec. .
- a pure water contact time parameter can be adopted as an index for selecting the conditions of the transfer pipe. This is a parameter calculated from the surface area and time of contact with the transfer pipe when pure water passes through the 1-meter long transfer pipe, and is calculated by the following calculation formula.
- V Flow velocity R: Transfer pipe radius
- a known measurement method may be used.
- a method of installing and measuring a current meter such as a commercially available electromagnetic current meter or propeller type current meter in a pipe flow path, and (ii) after measuring the flow rate of water flowing in the pipe, And a method for calculating the flow velocity.
- Flow velocity (m / sec) Flow rate (m 3 / sec) / Pipe cross section (m 2 )
- a known measurement method may be used as a method for measuring the flow rate.
- a method of installing and measuring a flow meter such as a commercially available electromagnetic flow meter or an ultrasonic flow meter in a pipe flow path
- measuring the volume of water discharged from the pipe during a certain period of time For example, a method for calculating a flow rate per unit time may be used.
- the pure water contact time parameter (CT) is preferably 1.0 ⁇ 10 2 seconds / m 2 to 3.0 ⁇ 10 5 seconds / m 2 , and more preferably 1.2 ⁇ 10 2 seconds / m 2 to It is 2.5 ⁇ 10 5 seconds / m 2 , more preferably 1.2 ⁇ 10 2 seconds / m 2 to 1.5 ⁇ 10 5 seconds / m 2 .
- pure water contact time parameter (CT) and 3.0 ⁇ 10 5 sec / m 2 or less it is possible to suppress the mixing of impurities from the transfer pipe, to polymerize the more stably the copolymer It is considered possible.
- the pure water contact time parameter (CT) is 1.0 ⁇ 10 2 sec / m 2 or more.
- the copolymer can be stably polymerized. If the pure water contact time parameter (CT) can be increased, it is advantageous in that the degree of freedom in piping design is increased.
- the flow velocity V means an instantaneous flow velocity.
- the pure water contact time parameter (CT) is preferably within the above range at 70% by volume or more of pure water transferred by this production method, and the pure water contact time parameter (CT) is at the above level at 90% by volume or more. More preferably, the pure water contact time parameter (CT) is more preferably within the above range at 95% by volume or more, and the pure water contact time parameter (CT) is within the above range at 100% by volume. It is particularly preferred.
- the polymerization step is a step of producing a specific copolymer (described in detail later) by polymerization in a reaction kettle.
- a transfer pipe used in the pure water transfer process is introduced into the reaction kettle used in the polymerization process.
- the material of the reaction kettle it is preferable to use a material with less elution of metal and impurities from the reaction kettle, specifically, those manufactured using stainless steel or Hastelloy, or those whose surface is glass-lined. Is used.
- the conductivity of the pure water is measured at a location where the pure water is introduced from the transfer pipe to the reaction kettle side, and is set within the range of 0.1 ⁇ S / cm to 100 ⁇ S / cm.
- a specific copolymer (described in detail later) is obtained. In the production of), a copolymer can be stably produced when water for polymerization with few impurities is prepared and used in the pure water production process.
- the conductivity of the pure water at a location where pure water is introduced from the transfer pipe to the reaction kettle side is 0. Even when it is out of the range of 1 ⁇ S / cm to 100 ⁇ S / cm, the copolymer can be stably produced.
- the conductivity of the pure water at a location where the pure water is introduced from the transfer pipe to the reaction kettle side is 0.1 ⁇ S / cm to 100 ⁇ S / cm. If it is not within the range, the copolymer cannot be produced stably.
- pure water having an electrical conductivity of 0.1 ⁇ S / cm to 100 ⁇ S / cm is produced in the pure water production process, In the transfer step, it is introduced into the reaction kettle through a transfer pipe made of a resin or a substance that forms a passive state in water, and further, the pure water is introduced into the reaction kettle side from the transfer pipe. Unless the conductivity of the pure water is within the range of 0.1 ⁇ S / cm to 100 ⁇ S / cm, a copolymer cannot be produced stably.
- the conductivity of the pure water at the place where the pure water is introduced from the transfer pipe to the reaction kettle side is 0.1 ⁇ S / cm to 100 ⁇ S / cm, preferably 0.1 ⁇ S / cm to 80 ⁇ S / cm, More preferably, it is 0.1 ⁇ S / cm to 60 ⁇ S / cm, still more preferably 0.1 ⁇ S / cm to 40 ⁇ S / cm, and particularly preferably 0.1 ⁇ S / cm to 20 ⁇ S / cm.
- the polymerization step is a step of polymerizing a monomer composition containing the monomer (a), the monomer (b), and the monomer (c). In this step, polymerization is performed in a reaction kettle. To produce a specific copolymer.
- This specific copolymer includes 50% to 99% by weight of the structural unit (I) derived from the unsaturated polyalkylene glycol ether monomer (a) represented by the general formula (1), and the general formula (2).
- the unsaturated polyalkylene glycol ether monomer (a) represented by the general formula (1) may be only one type or two or more types.
- the unsaturated monocarboxylic acid monomer (b) represented by the general formula (2) may be only one type or two or more types.
- the monomer (c) may be only one type or two or more types.
- the total of the structural unit (I), the structural unit (II), and the structural unit (III) is 100% by weight.
- the ratio of the structural unit (I) to the structural unit (II) is preferably a molar ratio of the structural unit (I) ⁇ the structural unit (II), more preferably the molar ratio of the structural unit (I). / Structural unit (II) ⁇ 0.95, more preferably in molar ratio, structural unit (I) / structural unit (II) ⁇ 0.90, and particularly preferably in molar ratio, structural unit ( I) / structural unit (II) ⁇ 0.85, and most preferably, the molar ratio is structural unit (I) / structural unit (II) ⁇ 0.80.
- Y 1 represents CH 2 ⁇ CR 0 — (CH 2 ) m —
- R 0 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- m is an integer of 0 to 2 is there.
- R 0 is a hydrogen atom or a methyl group.
- a vinyl group, 2-propenyl group (allyl group), 2-methyl-2-propenyl group (methallyl group), and 3-methyl-3-butenyl group (isoprenyl group) are more preferable.
- 2-methyl-2-propenyl group (methallyl group) and 3-methyl-3-butenyl group (isoprenyl group) are more preferable.
- 2-methyl-2-propenyl group (methallyl group) and 3-methyl-3-butenyl group (isoprenyl group) more preferably 3-methyl-3-butenyl group (isoprenyl group).
- R 1 O represents one or more oxyalkylene groups having 2 to 18 carbon atoms.
- the oxyalkylene group preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms.
- R 1 O examples include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxystyrene group. Among these, an oxyethylene group, an oxypropylene group, and an oxybutylene group are preferable, and an oxyethylene group and an oxypropylene group are more preferable. In addition, when two or more different R 1 O structures exist, these different R 1 O structures may exist in any form such as random addition, block addition, and alternate addition. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable that an oxyethylene group contains an oxyethylene group as an essential component.
- 50 mol% or more is preferably an oxyethylene group, more preferably 80 mol% or more is an oxyethylene group, and more preferably 90 mol% or more with respect to 100 mol% of all oxyalkylene groups.
- An oxyethylene group is particularly preferable, and 100 mol% is particularly preferably an oxyethylene group.
- n is the average number of moles added of the oxyalkylene group, and is greater than 0 and 500 or less. n is preferably 2 to 250, more preferably 3 to 200, still more preferably 4 to 150, and particularly preferably 5 to 75.
- the “average number of moles added” means the average number of moles of oxyalkylene groups added in 1 mole of the compound.
- R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
- hydrocarbon group having 1 to 30 carbon atoms examples include an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkyl having 7 to 30 carbon atoms. Groups.
- the alkyl group having 1 to 30 carbon atoms may be a linear, branched, or cyclic alkyl group.
- the alkyl group having 1 to 30 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group, and more preferably a methyl group, an ethyl group, or an n-group.
- the alkyl group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
- aryl group having 6 to 30 carbon atoms examples include a phenyl group, an alkylphenyl group, a phenyl group substituted with an alkylphenyl group, and a naphthyl group. Further, the aryl group having 6 to 30 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.
- Examples of the aralkyl group having 7 to 30 carbon atoms include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, styryl group (Ph—CH ⁇ C— group). ), Cinnamyl group (Ph—CH ⁇ CHCH 2 — group), 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group.
- R 2 is a substituted aryl group having 6 to 30 carbon atoms or a substituted aralkyl group having 7 to 30 carbon atoms
- substituents include alkyl having 1 to 3 carbon atoms.
- unsaturated polyalkylene glycol ether monomer (a) represented by the general formula (1) include polyethylene glycol mono (3-methyl-3-butenyl) ether, polyethylene glycol mono (3- Methyl-2-butenyl) ether, polyethylene glycol mono (2-methyl-3-butenyl) ether, polyethylene glycol mono (2-methyl-2-butenyl) ether, polyethylene glycol mono (1,1-dimethyl-2-propenyl) Ether, polyethylene polypropylene glycol mono (3-methyl-3-butenyl) ether, methoxypolyethylene glycol mono (3-methyl-3-butenyl) ether, ethoxypolyethylene glycol mono (3-methyl-3-butenyl) ether, 1-propoxy Poly Tylene glycol mono (3-methyl-3-butenyl) ether, cyclohexyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, 1-octyloxypolyethylene glycol mono (3-
- the unsaturated polyalkylene glycol ether monomer (a) represented by the general formula (1) is preferably allyl alcohol, 3-methyl-3-buten-1-ol, 2-methyl-2-propene.
- -1-ol (methallyl alcohol), a compound obtained by adding alkylene oxide to vinyl alcohol, more preferably polyethylene glycol mono (3-methyl-3-butenyl) ether, polyethylene glycol mono (2-methyl-2) -Propenyl) ether.
- R 3 , R 4 , and R 5 are the same or different and are a hydrogen atom or a methyl group.
- M represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group.
- the unsaturated monocarboxylic acid monomer (b) represented by the general formula (2) is preferably a (meth) acrylic acid monomer. Specific examples include acrylic acid, methacrylic acid, crotonic acid, and monovalent metal salts, divalent metal salts, ammonium salts, organic ammonium salts, and organic amine salts thereof. From the viewpoint of copolymerization, the unsaturated monocarboxylic acid monomer (b) represented by the general formula (2) is preferably (meth) acrylic acid and / or a salt thereof, more preferably. Is acrylic acid and / or a salt thereof.
- the ratio of the unsaturated polyalkylene glycol ether monomer (a) to the unsaturated monocarboxylic acid monomer (b) is preferably a weight ratio of ⁇ the monomer (b) / (the monomer The monomer (a) + the monomer (b)) ⁇ ⁇ 100 ⁇ 5.8.
- Unsaturated cyanides Unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethyl (meth) acrylate
- Unsaturated amines such as aminopropyl, dibutylaminoethyl (meth) acrylate and vinylpyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth) allyl alcohol and glycidyl (meth) allyl Allyls such as ether; Unsaturated amino compounds such as tilaminoethyl (meth) acrylate; polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminomaleamic acid, polydimethylsiloxane
- the monomer (c) is preferably an unsaturated dicarboxylic acid monomer such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and / or a salt thereof. More preferred are ⁇ , ⁇ -unsaturated dicarboxylic acid monomers such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and / or their salts.
- the weight average molecular weight of the copolymer is preferably 10,000 to 300,000, more preferably 10,000 to 100,000, still more preferably 10,000 to 80,000, and particularly preferably 10,000 in terms of polyethylene glycol by gel permeation chromatography. ⁇ 70,000.
- the copolymer has a weight average molecular weight variation coefficient CV of preferably 0.04 or less, and more preferably 0.03 or less.
- the variation coefficient CV will be described in detail later.
- the coefficient of variation CV is an index of variation, and the smaller the value, the higher the polymerization reproducibility. In an actual plant, it may be applied to the coefficient of variation CV of the weight average molecular weight between batches, and is preferably applied to the coefficient of variation CV of three consecutive batches.
- the resulting copolymer has a weight average molecular weight of 10,000 to 300,000 (in terms of polyethylene glycol by gel permeation chromatography). It is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, and still more preferably 10,000 to 70,000.
- the coefficient of variation CV of the weight average molecular weight of the resulting copolymer is 0.04 or less ( Preferably it is 0.03 or less.
- a copolymer is produced by polymerization in a reaction kettle. Specifically, it is produced by polymerizing a monomer as a raw material of the copolymer in a reaction kettle. More specifically, for example, an unsaturated polyalkylene glycol ether monomer (a) represented by general formula (1) and an unsaturated monocarboxylic acid monomer represented by general formula (2) ( It is produced by copolymerizing a monomer component containing b) as an essential component.
- unsaturated polyalkylene glycol ether monomer (a) represented by the general formula (1) instead of the unsaturated polyalkylene glycol ether monomer (a) represented by the general formula (1), a monomer before addition of alkylene oxide or polyalkylene glycol, that is, 3-methyl Unsaturated alcohols such as -3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, etc. were used, and these were used in the presence of a polymerization initiator.
- the copolymer can also be obtained by a method of reacting an alkoxypolyalkylene glycol, and this method can also be employed in the polymerization step.
- the copolymerization method can be carried out by any appropriate method such as solution polymerization using water as an essential solvent.
- the solution polymerization can be carried out either batchwise or continuously.
- the solvent that can be used in the solution polymerization include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane; Etc.
- the solvent that can be used in the solution polymerization is preferably water.
- water-soluble polymerization initiators such as persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; 2,2'- Azoamidine compounds such as azobis-2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoylazoisobutyronitrile, etc.
- persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate
- hydrogen peroxide hydrogen peroxide
- 2,2'- Azoamidine compounds such as azobis-2-methylpropionamidine hydrochloride
- cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoylazoisobutyronitrile, etc.
- Water-soluble azo initiators such as azonitrile compounds of These polymerization initiators include alkali metal sulfites such as sodium hydrogen sulfite, metabisulfites, sodium hypophosphite, Fe (II) salts such as molle salts, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride Accelerators such as salts, thiourea, L-ascorbic acid (salt), erythorbic acid (salt) can also be used in combination. Among these combined forms, a combination of hydrogen peroxide or ammonium persulfate with an accelerator such as L-ascorbic acid (salt) is preferable. Each of these polymerization initiators and accelerators may be only one kind or two or more kinds.
- peroxides such as benzoyl peroxide, lauroyl peroxide, sodium peroxide; t-butyl hydroperoxide, cumene hydroperoxide Hydroperoxides such as azo compounds; azo compounds such as azobisisobutyronitrile; and the like.
- an accelerator such as an amine compound can be used in combination.
- water-lower alcohol mixed solvent it can be appropriately selected from the above-mentioned various polymerization initiators or combinations of polymerization initiators and accelerators.
- the reaction temperature for the polymerization of the monomer component is appropriately determined depending on the polymerization method, solvent, polymerization initiator, and chain transfer agent used. Such a reaction temperature is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, preferably 100 ° C. or lower, more preferably 90 ° C. or lower. And more preferably 80 ° C. or lower.
- any appropriate method can be adopted as a method for charging the monomer component into the reaction vessel (reaction kettle).
- Such charging methods include, for example, a method in which the entire amount is initially charged into the reaction vessel (reaction kettle), a method in which the entire amount is divided or continuously charged into the reaction vessel (reaction kettle), and a part of the reaction vessel (reaction kettle). ) In the initial stage and the remainder is divided or continuously charged into a reaction vessel (reaction kettle).
- the charging rate of each monomer into the reaction vessel (reaction kettle) is changed continuously or stepwise to change the charging mass ratio of each monomer per unit time continuously or stepwise. You may let them.
- the polymerization initiator may be charged into the reaction vessel (reaction vessel) from the beginning, may be dropped into the reaction vessel (reaction vessel), or may be combined in accordance with the purpose. It should be noted that water initially charged in a reaction vessel (reaction kettle), water used for charging monomer components, polymerization initiator, accelerator, chain transfer agent (described later) and other additives are used.
- the water is also preferably pure water obtained in the pure water production step, that is, all water used in the polymerization step is preferably pure water obtained in the pure water production step.
- a chain transfer agent can be preferably used.
- a chain transfer agent When a chain transfer agent is used, the molecular weight of the resulting copolymer can be easily adjusted. Only one type of chain transfer agent may be used, or two or more types may be used.
- chain transfer agent Any appropriate chain transfer agent may be employed as the chain transfer agent.
- chain transfer agents include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; Secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, And lower salts of salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof, etc. Is mentioned.
- the pH of the reaction solution after the production of the copolymer is adjusted to 5 or more from the viewpoint of handleability.
- the pH can be adjusted, for example, using an alkaline substance such as an inorganic salt such as monovalent metal or divalent metal hydroxide or carbonate; ammonia; organic amine;
- the concentration of the produced copolymer can be adjusted as necessary with respect to the solution obtained by the production.
- the produced copolymer may be used as it is in the form of a solution, or may be neutralized with a divalent metal hydroxide such as calcium or magnesium to obtain a polyvalent metal salt and then dried,
- the powder may be used by being supported on an inorganic powder such as silica-based fine powder and dried.
- the cumulative charge ratio of the unsaturated monocarboxylic acid monomer (b) to the reaction kettle (monomer (b)
- the cumulative charge ratio of the unsaturated polyalkylene glycol ether monomer (a) to the reaction kettle relative to the total charged amount of the monomer (b) (monomer (a) It is preferable that there is a point in time when there is a large amount of the monomer (a) already charged relative to the total amount of the monomer (a). Specifically, the following method is exemplified.
- a part of the monomer (a) is charged into the reaction vessel before the start of polymerization, and the remainder of the monomer (a) and the monomer (b) after the start of charging the polymerization initiator into the reaction vessel A method in which the total amount of is divided or continuously charged into the reaction kettle.
- a part of the monomer (a) and a part of the monomer (b) are charged into the reaction kettle before the start of polymerization, and the monomer (a ) And the remainder of monomer (b) are divided or continuously charged into the reaction kettle, and the monomer (b) reaction kettle at the end of charging of monomer (a) into the kettle The method of delaying the end of charging.
- the monomer (a) and the monomer (a) have a low polymerizability, although the monomer (a) has a lower polymerizability than the monomer (b). It becomes possible to efficiently copolymerize the monomer (b).
- the method for charging the monomer (c) into the reaction kettle is not particularly limited. A method in which the entire amount is initially charged into the reaction kettle, a method in which the entire amount is divided or continuously charged into the reaction kettle, and a part of the reaction kettle is charged. Any of the methods may be employed in which the initial charging is performed and the remainder is divided into the reaction kettle or continuously charged.
- the neutralization rate of the monomer (b) and the monomer (c) is not particularly limited, and the neutralization rate may be changed so as not to affect the polymerization initiator, the chain transfer agent and the like.
- the polymerization reaction is carried out under such conditions, and after completion of the reaction, neutralization and concentration adjustment are performed as necessary.
- the ratio of each monomer used in producing the copolymer is not particularly limited as long as the monomer (a) and the monomer (b) are essential, and preferably the monomer.
- the total of the monomer (a), the monomer (b), and the monomer (c) is 100% by weight.
- the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
- the term “part” means “part by weight”, and “%” means “% by weight”.
- weight is synonymous with “mass” which means weight. Therefore, “weight” may be read as “mass”, and “mass” may be read as “weight”.
- ⁇ GPC measurement conditions The measurement was performed under the following conditions.
- Eluent A solution prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and adjusting the pH to 6.0 with acetic acid is used.
- the coefficient of variation CV is an index of variation, and the smaller the value, the higher the polymerization reproducibility.
- the value of the coefficient of variation CV is preferably 0.04 or less, and more preferably 0.03 or less. In an actual plant, it may be applied to the coefficient of variation CV of the weight average molecular weight between batches, and is preferably applied to the coefficient of variation CV of three consecutive batches.
- Table 1 when the coefficient of variation CV was 0.03 or less, the best (A) was given, and when the coefficient of variation CV was more than 0.03 and 0.04 or less, it was judged as good ( ⁇ ).
- the case where it exceeded 0.04 and 0.05 or less was set to (triangle
- Example 1 Tap water with a conductivity of 154.8 ⁇ S / cm, using distilled water production equipment (RFD342NA, ADVANTEC), one pretreatment cartridge filter (RF000141, Advantech), ion exchange resin cartridge (RF000131, Advantech) 2) and one hollow fiber filter (RF000220, manufactured by Advantech) at a flow rate of 1 L / min to produce pure water (1) having a conductivity of 0.67 ⁇ S / cm. . (Pure water storage process) 10 kg of pure water (1) produced in the pure water production process was stored in a polypropylene container.
- the pure water (1) stored in the pure water storage step is transferred to a transfer pipe made of SUS304 (inner diameter 10.5 mm, length 10 m) using a pump A (manufactured by Tsurumi Seisakusho, FP-5S) at a flow rate of 1.0 m / Circulated for 1 hour in seconds.
- the conductivity of the pure water (1) discharged from the transfer pipe after circulation was 0.80 ⁇ S / cm.
- the pure water contact time parameter (CT) under these transfer conditions was 1.1 ⁇ 10 5 seconds / m 2 .
- CT calculation method of the pure water contact time parameter (CT) is as follows.
- Example 2 By changing the transfer pipe made of SUS304 used in the pure water transfer process to a transfer pipe made of SUS316 (inner diameter 10.5 mm, length 10 m), the conductivity of pure water (2) discharged from the transfer pipe after circulation is 0. A copolymer (2) was obtained in the same manner as in Example 1 except that the concentration was 0.83 ⁇ S / cm.
- Example 3 Conductivity of pure water (3) discharged from the transfer pipe after circulation by changing the transfer pipe made of SUS304 used in the pure water transfer process to a transfer pipe made of polyvinyl chloride (inner diameter 10.0 mm, length 10 m) was carried out in the same manner as in Example 1 except that the value became 0.75 ⁇ S / cm, to obtain a copolymer (3).
- Example 4 Pur water production process
- Pure water (1) having an electrical conductivity of 0.67 ⁇ S / cm manufactured in the pure water manufacturing process of Example 1 and tap water having an electrical conductivity of 154.8 ⁇ S / cm are mixed at a mass ratio of 9/1.
- pure water (4) having an electric conductivity of 18.50 ⁇ S / cm was produced.
- Pure water storage process 10 kg of pure water (4) produced in the pure water production process was stored in a polypropylene container.
- Example 5 Purge water production process
- Pure water (1) having an electrical conductivity of 0.67 ⁇ S / cm manufactured in the pure water manufacturing process of Example 1 and tap water having an electrical conductivity of 154.8 ⁇ S / cm are mixed at a mass ratio of 8/2.
- pure water (5) having a conductivity of 34.39 ⁇ S / cm was produced.
- Pure water storage process 10 kg of pure water (5) produced in the pure water production process was stored in a polypropylene container.
- Pure water transfer process Using the pump A, the pure water (5) stored in the pure water storage step was circulated through a transfer pipe made of SUS304 (inner diameter 10.5 mm, length 10 m) at a flow rate of 1.0 m / second for 1 hour.
- Example 6 In the pure water transfer step of Example 1, the time for circulating in the pipe made of SUS304 was extended to 2 hours.
- the conductivity of pure water (1-b) discharged from the transfer pipe after circulation was 0.82 ⁇ S / cm.
- the pure water contact time parameter (CT) under these transfer conditions was 2.2 ⁇ 10 5 seconds / m 2 .
- the calculation method of the pure water contact time parameter (CT) is as follows.
- a copolymer (6) was obtained by carrying out the same polymerization as in Example 1 except that the pure water used for the polymerization was changed to the pure water (1-b) discharged from the transfer pipe. The results are shown in Table 1.
- Example 7 Pure water transferred to a glass reaction vessel (reaction kettle) equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser using a transfer pipe made of SUS304 in the pure water transfer step of Example 1.
- reaction kettle glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser using a transfer pipe made of SUS304 in the pure water transfer step of Example 1.
- Example 8 Pure water transferred to a glass reaction vessel (reaction kettle) equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser using a transfer pipe made of SUS304 in the pure water transfer step of Example 1.
- reaction kettle glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser using a transfer pipe made of SUS304 in the pure water transfer step of Example 1.
- Example 9 Pure water having an electrical conductivity of 0.40 ⁇ S / cm obtained by distilling tap water was transferred to a SUS304 transfer pipe (inner diameter 28 mm, length 75 m) using a pump B (manufactured by Aihara Seisakusho Co., Ltd., 40 ⁇ 25 IFWM type) at 3 m / Transferred at a flow rate of seconds for 25 seconds.
- the conductivity of pure water (6) collected from this pipe was 0.40 ⁇ S / cm.
- the pure water contact time parameter (CT) under the transfer conditions was 2.8 ⁇ 10 2 seconds / m 2 .
- the calculation method of the pure water contact time parameter (CT) is as follows.
- Example 10 In a glass reaction vessel (reaction kettle) equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, the pure water production process, the pure water storage process, and the pure water transfer process described in Example 1 were performed. 122.8 g of the obtained pure water (1), 205.3 g of unsaturated alcohol obtained by adding 50 moles of ethylene oxide to methallyl alcohol were charged, and the reaction vessel (reaction vessel) was purged with nitrogen under stirring. After raising the temperature to 65 ° C., 20.0 g of a 2% aqueous hydrogen peroxide solution was added all at once.
- Example 11 In a glass reaction vessel (reaction kettle) equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, the pure water production process, the pure water storage process, and the pure water transfer process described in Example 1 were performed. 170.0 g of the obtained pure water (1) and 91.5 g of unsaturated alcohol (total number of moles of added ethylene oxide of 25 mol) obtained by adding 23 mol of ethylene oxide to diethylene glycol monovinyl ether were charged, and the reaction vessel (reaction vessel) was stirred. ) Was replaced with nitrogen, and the temperature was raised to 40 ° C. in a nitrogen atmosphere.
- unsaturated alcohol total number of moles of added ethylene oxide of 25 mol
- Example 1 A copolymer (C1) was obtained in the same manner as in Example 1 except that pure water (1) used in the polymerization step was changed to tap water (conductivity was 154.8 ⁇ S / cm). . The results are shown in Table 2.
- Example 2 In Example 1, by changing the transfer pipe made of SUS304 used for the pure water transfer process to a transfer pipe made of carbon steel (inner diameter 10.5 mm, length 10 m), pure water discharged from the transfer pipe after circulation (1 ) was conducted in the same manner as in Example 1 except that the conductivity was 0.97 ⁇ S / cm to obtain a copolymer (C2). The results are shown in Table 2.
- Comparative Example 3 In the pure water transfer step of Comparative Example 2, the time for circulating in the carbon steel pipe was extended to 2 hours. The conductivity of the pure water (1-c) discharged from the transfer pipe after circulation was 1.25 ⁇ S / cm. A copolymer (C3) was obtained by carrying out the same polymerization as in Example 1 except that the pure water used for the polymerization was changed to the pure water (1-c) discharged from the transfer pipe. The results are shown in Table 2.
- Example 10 In Example 10, it replaced with the tap water instead of the pure water (1) used at a superposition
- Example 10 instead of pure water (1) used in the polymerization step, the same procedure as in Example 10 was used except that pure water obtained using a transfer pipe made of carbon steel was used. C5) was obtained. The results are shown in Table 2.
- a monomer mixture aqueous solution was prepared by uniformly mixing 0.3 g of a 30% aqueous sodium hydroxide solution and 0.6 g of mercaptopropionic acid as a chain transfer agent. While the monomer mixture aqueous solution was dropped over 4 hours, an aqueous solution prepared by dissolving 0.8 g of ammonium persulfate in 49.2 g of pure water (1) discharged in the pure water transfer step was dropped over 5 hours.
- Reference Example 3 In Reference Example 1, by changing the transfer pipe made of SUS304 used in the pure water transfer process to a transfer pipe made of carbon steel (inner diameter 10.5 mm, length 10 m), pure water discharged from the transfer pipe after circulation (1 The copolymer (R3) was obtained in the same manner as in Reference Example 1 except that the electrical conductivity was 0.97 ⁇ S / cm. The results are shown in Table 2.
- Comparative Examples 2, 3, and 5 even when water having a conductivity of 0.1 ⁇ S / cm to 100 ⁇ S / cm is used in the pure water manufacturing process, the water discharged from the transfer pipe is also used. Even if the conductivity is 0.1 ⁇ S / cm to 100 ⁇ S / cm, the polymerization reproducibility is inferior when transported through a carbon steel pipe that is not made of a resin or a substance that forms a passive state in water. It became. Further, as is clear from Examples 1 and 6, when a SUS pipe, which is a material that forms a passive state, is used, there is little decrease in polymerization stability even when the contact time of the transfer pipe and pure water is increased. It was. On the other hand, as is clear from Comparative Examples 2 and 3, when the carbon steel pipe was used, the polymerization stability was greatly lowered by increasing the contact time between the transfer pipe and the pure water.
- the conductivity in the pure water production process, the material of the transfer pipe Does not affect the reproducibility of the copolymer. That is, as shown in the Examples and Comparative Examples in Tables 1 and 2, in the production of the specific copolymer specified in the present invention, the conductivity is 0.1 ⁇ S / cm to 100 ⁇ S / cm in the pure water production process. It can be understood that the copolymer cannot be stably produced unless the pure water is produced and introduced into the reaction kettle through a transfer pipe made of a specific material in the pure water transfer step.
- the copolymer obtained by the production method of the present invention can be used, for example, as a cement admixture.
Abstract
Description
一般式(1)で表される不飽和ポリアルキレングリコールエーテル系単量体(a)由来の構造単位(I)50重量%~99重量%と、一般式(2)で表される不飽和モノカルボン酸系単量体(b)由来の構造単位(II)1重量%~50重量%と、該単量体(a)および/または該単量体(b)と共重合可能な単量体(c)由来の構造単位(III)0重量%~49重量%(ただし、構造単位(I)、構造単位(II)、および構造単位(III)の合計は100重量%である)とを有する共重合体の製造方法であって、
導電率が0.1μS/cm~100μS/cmの純水を製造する純水製造工程と、該共重合体を製造するための反応釜に該純水を、樹脂、または、水中で不動態を形成する物質を材質とする移送配管によって導入する純水移送工程と、該反応釜中で、該単量体(a)、単量体(b)および単量体(c)の重合を行う重合工程とを含み、該純水移送工程において、該純水が該移送配管から該反応釜側に導入される箇所での該純水の導電率を0.1μS/cm~100μS/cmの範囲内とすることを特徴とする。
純水接触時間パラメータ(CT)= T/S
T=L/V
S=2π×R
T:移送配管1メートルあたりの純水が移送配管に接触する時間
S:移送配管1メートルあたりの純水接触表面積
L:移送配管長(純水が移送配管と接触する長さ)
V:流速
R:移送配管半径
流速Vの測定方法としては公知の測定方法を用いればよい。例えば、(i)市販の電磁流速計やプロペラ式流速計などの流速計を配管流路中に設置し測定する方法、(ii)配管中を流れる水の流量を測定した後、下記の式より流速を算出する方法、などが挙げられる。
流速(m/秒)=流量(m3/秒)/配管断面積(m2)
また、流量を測定する方法についても公知の測定方法を用いればよい。例えば、(i)市販の電磁流量計や超音波流量計などの流量計を配管流路中に設置し測定する方法、(ii)一定時間中に配管より排出された水の体積を実測し、単位時間当たりの流量を算出する方法、などが挙げられる。
(i)単量体(a)の全量を重合開始前に反応釜に一括投入し、重合開始剤の反応釜への投入開始以後に単量体(b)の全量を反応釜に分割もしくは連続投入する方法。
(ii)単量体(a)の全量と単量体(b)の一部を重合開始前に反応釜に投入し、重合開始剤の反応釜への投入開始以後に単量体(b)の残りを反応釜に分割もしくは連続投入する方法。
(iii)単量体(a)の一部を重合開始前に反応釜に投入し、重合開始剤の反応釜への投入開始以後に単量体(a)の残りと単量体(b)の全量を反応釜に分割もしくは連続投入する方法。
(iv)単量体(a)の一部と単量体(b)の一部を重合開始前に反応釜に投入し、重合開始剤の反応釜への投入開始以後に単量体(a)の残りと単量体(b)の残りを反応釜に分割もしくは連続投入し、かつ、単量体(a)の反応釜への投入終了時点に対して単量体(b)の反応釜への投入終了時点が遅れる方法。
(v)単量体(a)の一部と単量体(b)の一部を重合開始前に反応釜に投入し、重合開始剤の反応釜への投入開始以後に単量体(a)の残りと単量体(b)の残りを反応釜に分割もしくは連続投入し、かつ、単量体(b)の反応釜への累積投入割合(単量体(b)の全投入量に対する、投入済みの単量体(b)の重量%)に対し、単量体(a)の反応釜への累積投入割合(単量体(a)の全投入量に対する、投入済みの単量体(a)の重量%)が多い時点が存在する方法。
(vi)重合開始剤の反応釜への投入開始以後に単量体(a)の全量と単量体(b)の全量を反応釜に分割もしくは連続投入し、かつ、単量体(b)の反応釜への累積投入割合(単量体(b)の全投入量に対する、投入済みの単量体(b)の重量%)に対し、単量体(a)の反応釜への累積投入割合(単量体(a)の全投入量に対する、投入済みの単量体(a)の重量%)が多い時点が存在する方法。
下記の条件で測定した。
使用カラム:東ソー社製、TSK guard column SWXL+TSKgel G4000SWXL+G3000SWXL+G2000SWXL
溶離液:水10999g、アセトニトリル6001gの混合溶媒に酢酸ナトリウム三水和物115.6gを溶解し、さらに酢酸でpH6.0に調整した溶液を使用。
サンプル打ち込み量:100μL
流速:1.0mL/min
カラム温度:40℃
検出器:日本ウォーターズ社製、2414 示差屈折検出器
解析ソフト:日本ウォーターズ社製、Empower Software+GPCオプション
較正曲線作成用標準物質:ポリエチレングリコール[ピークトップ分子量(Mp)272500、219300、107000、50000、24000、12600、7100、4250、1470]
較正曲線:上記ポリエチレングリコールのMp値と溶出時間とを基礎にして3次式で作成した。
サンプル:重合体水溶液を上記溶離液で重合体濃度が0.5重量%となるように溶解させたものをサンプルとした。
得られたRIクロマトグラムにおいて、ポリマー溶出直前・溶出直後のベースラインにおいて平らに安定している部分を直線で結び、ポリマーを検出・解析した。ただし、モノマー、モノマー由来の不純物等がポリマーピークに一部重なって測定された場合、それらとポリマーとの重なり部分の最凹部において垂直分割してポリマー部とモノマー部とを分離し、ポリマー部のみの分子量・分子量分布を測定した。ポリマー部とそれ以外とが完全に重なり分離できない場合はまとめて計算した。
25℃の恒温槽にて調温したサンプル水を、HORIBA社製の低電気導電率用セル「3551-10D」を装着したHORIBA社製のpHメーター「D-54」を用いて、導電率を測定した。
同じ条件の重合を3回行い、得られた共重合体の重量平均分子量の変動係数CVを下記式によって求めた。
(純水製造工程)
導電率が154.8μS/cmの水道水を、蒸留水製造装置(RFD342NA、ADVANTEC社製)を用い、前処理カートリッジフィルター(RF000141、アドバンテック社製)を1本、イオン交換樹脂カートリッジ(RF000131、アドバンテック社製)を2本、中空糸フィルター(RF000220、アドバンテック社製)を1本、1L/minの流量で通過させることにより、導電率が0.67μS/cmである純水(1)を製造した。
(純水保管工程)
上記純水製造工程で製造した純水(1)を、ポリプロピレン製容器に10kg保管した。
(純水移送工程)
上記純水保管工程で保管した純水(1)を、ポンプA(鶴見製作所製、FP-5S)を用いてSUS304製の移送配管(内径10.5mm、長さ10m)に流速1.0m/秒で1時間循環させた。循環後に移送配管から排出した純水(1)の導電率は0.80μS/cmであった。この移送条件における純水接触時間パラメータ(CT)は1.1×105秒/m2であった。
なお、純水接触時間パラメータ(CT)の算出方法は下記の通りである。
純水を移送配管に流速1.0m/秒で1時間循環させたことから移送配管長(純水が移送配管と接触する長さ)は、
L=1.0(m/秒)×3600(秒)=3600(m)となり、
T=L/V=3600/1=3600(秒)
S=2π×R=2×3.14×(0.0105/2)=0.03297(m2)
CT=T/S=3600/0.03297=1.1×105(秒/m2)
(重合工程)
温度計、攪拌機、滴下ロート、窒素導入管および還流冷却器を備えたガラス製反応容器(反応釜)に、上記純水移送工程において排出した純水(1)96.4g、3-メチル-3-ブテン-1-オールにエチレンオキサイドを50モル付加した不飽和アルコール225.0gを仕込み、撹拌下に反応容器(反応釜)を窒素置換し、窒素雰囲気下で58℃に昇温した後、そこへ過酸化水素2%水溶液11.9gを一括で添加した。アクリル酸18.1gを純水(1)4.0gに溶解させた水溶液を4時間かけて滴下した。アクリル酸水溶液を滴下し始めると同時に、3-メルカプトプロピオン酸1.2g、L-アスコルビン酸0.5gを純水(1)41.1gに溶解させた水溶液を4.5時間かけて滴下した。その後、60分間引き続いて58℃に温度を維持して重合反応を完結させ、温度を50℃以下に降温し、30%水酸化ナトリウム水溶液でpH4からpH7になるように中和し、共重合体(1)を得た。
結果を表1に示した。
純水移送工程に用いるSUS304製の移送配管をSUS316製の移送配管(内径10.5mm、長さ10m)に変更することで、循環後に移送配管から排出した純水(2)の導電率が0.83μS/cmとなった以外は、実施例1と同様に行い、共重合体(2)を得た。
純水移送工程に用いるSUS304製の移送配管をポリ塩化ビニル製の移送配管(内径10.0mm、長さ10m)に変更することで、循環後に移送配管から排出した純水(3)の導電率が0.75μS/cmとなった以外は、実施例1と同様に行い、共重合体(3)を得た。
(純水製造工程)
実施例1の純水製造工程で製造した導電率が0.67μS/cmである純水(1)と、導電率が154.8μS/cmである水道水を質量比で9/1で混合させることにより、導電率が18.50μS/cmである純水(4)を製造した。
(純水保管工程)
上記純水製造工程で製造した純水(4)を、ポリプロピレン製容器に10kg保管した。
(純水移送工程)
上記純水保管工程で保管した純水(4)を、ポンプAを用いてSUS304製の移送配管(内径10.5mm、長さ10m)に流速1.0m/秒で1時間循環させた。循環後に移送配管から排出した純水(4)の導電率は18.58μS/cmであった。
(重合工程)
重合に用いる純水を上記の移送配管から排出した純水(4)に変更した以外は、実施例1と同様の重合を行い、共重合体(4)を得た。結果を表1に示した。
(純水製造工程)
実施例1の純水製造工程で製造した導電率が0.67μS/cmである純水(1)と、導電率が154.8μS/cmである水道水を質量比で8/2で混合させることにより、導電率が34.39μS/cmである純水(5)を製造した。
(純水保管工程)
上記純水製造工程で製造した純水(5)を、ポリプロピレン製容器に10kg保管した。
(純水移送工程)
上記純水保管工程で保管した純水(5)を、ポンプAを用いてSUS304製の移送配管(内径10.5mm、長さ10m)に流速1.0m/秒で1時間循環させた。循環後に移送配管から排出した純水(5)の導電率は35.82μS/cmであった。
(重合工程)
重合に用いる純水を上記の移送配管から排出した純水(5)に変更した以外は、実施例1と同様の重合を行い、共重合体(5)を得た。結果を表1に示した。
実施例1の純水移送工程において、SUS304製配管内を循環させる時間を2時間に延長した。循環後に移送配管から排出した純水(1-b)の導電率は0.82μS/cmであった。この移送条件における純水接触時間パラメータ(CT)は2.2×105秒/m2であった。
なお、純水接触時間パラメータ(CT)の算出方法は下記の通りである。
純水を移送配管に流速1.0m/秒で2時間循環させたことから移送配管長(純水が移送配管と接触する長さ)は、
L=1.0(m/秒)×7200(秒)=7200(m)となり、
T=L/V=7200/1=7200(秒)
S=2π×R=2×3.14×(0.0105/2)=0.03297(m2)
CT=T/S=7200/0.03297=2.2×105(秒/m2)
重合に用いる純水を上記の移送配管から排出した純水(1-b)に変更した以外は、実施例1と同様の重合を行い、共重合体(6)を得た。結果を表1に示した。
温度計、攪拌機、滴下ロート、窒素導入管および還流冷却器を備えたガラス製反応容器(反応釜)に、実施例1の純水移送工程において、SUS304製の移送配管を用いて移送した純水(1)96.4g、3-メチル-3-ブテン-1-オールにエチレンオキサイドを50モル付加した不飽和アルコール225.0gを仕込み、撹拌下に反応容器(反応釜)を窒素置換し、窒素雰囲気下で58℃に昇温した。続いて、アクリル酸18.1gを純水(1)4.0gに溶解させた水溶液を4時間で、過硫酸アンモニウム5.0gを純水(1)15.0gに溶解させた水溶液を4.5時間で、3-メルカプトプロピオン酸1.3gとL-アスコルビン酸0.5gを純水(1)30.0gに溶解させた水溶液を4.5時間で、それぞれ同時に一定速度で滴下した。その後、60分間引き続いて58℃に温度を維持して重合反応を完結させ、温度を50℃以下に降温し、30%水酸化ナトリウム水溶液でpH4からpH7になるように中和し、共重合体(7)を得た。結果を表1に示した。
温度計、攪拌機、滴下ロート、窒素導入管および還流冷却器を備えたガラス製反応容器(反応釜)に、実施例1の純水移送工程において、SUS304製の移送配管を用いて移送した純水(1)96.4g、3-メチル-3-ブテン-1-オールにエチレンオキサイドを50モル付加した不飽和アルコール225.0gを仕込み、撹拌下に反応容器(反応釜)を窒素置換し、窒素雰囲気下で58℃に昇温した。続いて、アクリル酸18.1gを純水(1)4.0gに溶解させた水溶液を4時間で、過酸化水素2%水溶液1.75gを純水(1)18.3gに溶解させた水溶液を4.5時間で、3-メルカプトプロピオン酸0.85gとL-アスコルビン酸0.09gを純水(1)30.0gに溶解させた水溶液を4.5時間で、それぞれ同時に一定速度で滴下した。その後、60分間引き続いて58℃に温度を維持して重合反応を完結させ、温度を50℃以下に降温し、30%水酸化ナトリウム水溶液でpH4からpH7になるように中和し、共重合体(8)を得た。結果を表1に示した。
水道水を蒸留することによって得られた導電率0.40μS/cmの純水を、ポンプB(在原製作所製、40X25IFWM型)を用いてSUS304製移送配管(内径28mm、長さ75m)を3m/秒の流速で25秒間で移送した。この配管から採取された純水(6)の導電率は0.40μS/cmであった。また、この移送条件における純水接触時間パラメータ(CT)は2.8×102秒/m2であった。
なお、純水接触時間パラメータ(CT)の算出方法は下記の通りである。
純水を移送配管に流速3.0m/秒で25秒間で移送したことから移送配管長(純水が移送配管と接触する長さ)は、
L=3.0(m/秒)×25(秒)=75(m)となり、
T=L/V=75/3=25(秒)
S=2π×R=2×3.14×(0.028/2)=0.08792(m2)
CT=T/S=25/0.08792=2.8×102(秒/m2)
重合に用いる純水を上記の純水(6)に変更した以外は、実施例1と同様の重合を行い、共重合体(9)を得た。結果を表1に示した。
温度計、攪拌機、滴下ロート、窒素導入管および還流冷却器を備えたガラス製反応容器(反応釜)に、実施例1に記載の純水製造工程、純水保管工程、純水移送工程を経て得られた純水(1)122.8g、メタリルアルコールにエチレンオキサイドを50モル付加した不飽和アルコール205.3gを仕込み、撹拌下に反応容器(反応釜)を窒素置換し、窒素雰囲気下で65℃に昇温した後、そこへ過酸化水素2%水溶液20.0gを一括で添加した。アクリル酸33.4gを純水(1)8.0gに溶解させた水溶液を3時間かけて滴下した。アクリル酸水溶液を滴下し始めると同時に、3-メルカプトプロピオン酸0.9g、L-アスコルビン酸0.5gを純水(1)25.3gに溶解させた水溶液を3.5時間かけて滴下した。その後、60分間引き続いて65℃に温度を維持して重合反応を完結させ、温度を50℃以下に降温し、30%水酸化ナトリウム水溶液でpH7になるように中和し、共重合体(10)を得た。結果を表1に示した。
温度計、攪拌機、滴下ロート、窒素導入管および還流冷却器を備えたガラス製反応容器(反応釜)に、実施例1に記載の純水製造工程、純水保管工程、純水移送工程を経て得られた純水(1)170.0g、ジエチレングリコールモノビニルエーテルにエチレンオキサイドを23モル付加した不飽和アルコール(エチレンオキサイド付加モル数合計25モル)91.5gを仕込み、撹拌下に反応容器(反応釜)を窒素置換し、窒素雰囲気下で40℃に昇温した。続いて、過酸化水素2%水溶液35.0gを1時間45分で、アクリル酸22.7gを純水(1)10.0gに溶解させた水溶液を1時間30分で、3-メルカプトプロピオン酸0.8g、L-アスコルビン酸0.9gを純水(1)70.0gに溶解させた水溶液を1時間45分で、それぞれ同時に一定速度で滴下した。その後、60分間引き続いて40℃に温度を維持して重合反応を完結させた。その後、30%水酸化ナトリウム水溶液でpH7になるように中和し、共重合体(11)を得た。結果を表1に示した。
実施例1において、重合工程に用いる純水(1)を水道水(導電率は154.8μS/cm)に変更した以外は、実施例1と同様に行い、共重合体(C1)を得た。
結果を表2に示した。
実施例1において、純水移送工程に用いるSUS304製の移送配管を炭素鋼製の移送配管(内径10.5mm、長さ10m)に変更することで、循環後に移送配管から排出した純水(1)の導電率が0.97μS/cmとなった以外は、実施例1と同様に行い、共重合体(C2)を得た。
結果を表2に示した。
比較例2の純水移送工程において、炭素鋼製配管内を循環させる時間を2時間に延長した。循環後に移送配管から排出した純水(1-c)の導電率は1.25μS/cmであった。重合に用いる純水を上記の移送配管から排出した純水(1-c)に変更した以外は、実施例1と同様の重合を行い、共重合体(C3)を得た。結果を表2に示した。
実施例10において、重合工程で用いる純水(1)の代わりに、水道水に変更した以外は、実施例10と同様に行い、共重合体(C4)を得た。結果を表2に示した。
実施例10において、重合工程で用いる純水(1)の代わりに、炭素鋼製の移送配管を用いて得られた純水を用いた以外は、実施例10と同様に行い、共重合体(C5)を得た。結果を表2に示した。
(純水製造工程)
導電率が154.8μS/cmの水道水を、蒸留水製造装置(RFD342NA、ADVANTEC社製)を用い、前処理カートリッジフィルター(RF000141、アドバンテック社製)を1本、イオン交換樹脂カートリッジ(RF000131、アドバンテック社製)を2本、中空糸フィルター(RF000220、アドバンテック社製)を1本、1L/minの流量で通過させることにより、導電率が0.67μS/cmである純水(1)を製造した。
(純水保管工程)
上記純水製造工程で製造した純水(1)を、ポリプロピレン製容器に10kg保管した。
(純水移送工程)
上記純水保管工程で保管した純水(1)を、ポンプAを用いてSUS304製の移送配管(内径10.5mm、長さ10m)に流速1.0m/秒で1時間循環させた。循環後に移送配管から排出した純水(1)の導電率は0.80μS/cmであった。
(重合工程)
温度計、撹拌機、滴下ロート、窒素導入管および還流冷却器を備えたガラス製反応容器(反応釜)に、上記純水移送工程において排出した純水(1)150.0gを仕込み、撹拌下に反応容器(反応釜)を窒素置換し、窒素雰囲気下で80℃まで加熱した。次に、メトキシポリエチレングリコールモノメタクリル酸エステル(エチレンオキシドの平均付加モル数45個)108.8g、メタクリル酸10.6g、および上記純水移送工程において排出した純水(1)65.5gを混合し、30%水酸化ナトリウム水溶液0.3g、さらに連鎖移動剤としてメルカプトプロピオン酸0.6gを均一に混合することにより、単量体混合物水溶液を調製した。この単量体混合物水溶液を4時間かけて滴下するとともに、過硫酸アンモニウム0.8gを上記純水移送工程において排出した純水(1)49.2gに溶解させた水溶液を5時間かけて滴下した。その後1時間引き続いて80℃に温度を維持し、溶液重合反応を完結させた。そして、30%水酸化ナトリウム水溶液でpH4からpH7になるように中和し、共重合体(R1)を得た。
結果を表2に示した。
参考例1において、重合工程に用いる純水(1)を水道水(導電率は154.8μS/cm)に変更した以外は、参考例1と同様に行い、共重合体(R2)を得た。
結果を表2に示した。
参考例1において、純水移送工程に用いるSUS304製の移送配管を炭素鋼製の移送配管(内径10.5mm、長さ10m)に変更することで、循環後に移送配管から排出した純水(1)の導電率が0.97μS/cmとなった以外は、参考例1と同様に行い、共重合体(R3)を得た。
結果を表2に示した。
また、実施例1および6から明らかなように、不動態を形成する材質であるSUS製配管を用いた場合は、移送配管と純水の接触時間が長くなっても重合安定性の低下は少なかった。一方、比較例2および3から明らかなように、炭素鋼製配管を用いた場合は、移送配管と純水の接触時間が長くなることにより、重合安定性が大きく低下した。
すなわち、表1および2の実施例・比較例に示すように、本発明で規定する特定の共重合体を製造するにあたっては、純水製造工程において導電率が0.1μS/cm~100μS/cmの純水を製造し、それを純水移送工程において特定の材質の移送配管によって反応釜に導入しなければ、安定的に共重合体を製造することができないことが判る。他方、参考例1~3に示すように、本発明で規定する特定の共重合体以外の重合体や共重合体を製造するにあたっては、重合に用いる純水を上記のように厳密に調整しなくても、共重合体の再現性には影響しないことが判る。
Claims (9)
- 一般式(1)で表される不飽和ポリアルキレングリコールエーテル系単量体(a)由来の構造単位(I)50重量%~99重量%と、一般式(2)で表される不飽和モノカルボン酸系単量体(b)由来の構造単位(II)1重量%~50重量%と、該単量体(a)および/または該単量体(b)と共重合可能な単量体(c)由来の構造単位(III)0重量%~49重量%(ただし、構造単位(I)、構造単位(II)、および構造単位(III)の合計は100重量%である)とを有する共重合体の製造方法であって、
導電率が0.1μS/cm~100μS/cmの純水を製造する純水製造工程と、該共重合体を製造するための反応釜に該純水を、樹脂、または、水中で不動態を形成する物質を材質とする移送配管によって導入する純水移送工程と、該反応釜中で、該単量体(a)、単量体(b)および単量体(c)の重合を行う重合工程とを含み、該純水移送工程において、該純水が該移送配管から該反応釜側に導入される箇所での該純水の導電率を0.1μS/cm~100μS/cmの範囲内とすることを特徴とする、共重合体の製造方法。
- 前記移送配管の材質が、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリエステルおよびテフロン(登録商標)からなる群より選ばれる少なくとも1種を含む樹脂、または、クロム、アルミニウムおよびチタンからなる群より選ばれる少なくとも1種を含む合金、から選ばれる少なくとも1種である、請求項1に記載の製造方法。
- 前記純水移送工程において、移送配管の長さL(m)と、純水の流速V(m/秒)と、移送配管の内半径R(m)とが、1.0×102秒/m2≦(L/V)/(2π×R)≦3.0×105秒/m2の関係を有する、請求項1または2に記載の製造方法。
- 前記一般式(1)中のY1を構成するR0が、水素原子またはメチル基である、請求項1から3のいずれかに記載の製造方法。
- 前記不飽和モノカルボン酸系単量体(b)が(メタ)アクリル酸系単量体である、請求項1から4までのいずれかに記載の製造方法。
- 前記不飽和ポリアルキレングリコールエーテル系単量体(a)と前記不飽和モノカルボン酸系単量体(b)との割合が、重量比で、{該単量体(b)/(該単量体(a)+該単量体(b))}×100≧5.8である、請求項1から5までのいずれかに記載の製造方法。
- 前記共重合体の重量平均分子量が、ゲルパーミエーションクロマトグラフィーによるポリエチレングリコール換算で、10000~300000である、請求項1から6までのいずれかに記載の製造方法。
- 同じ条件で前記共重合体の製造を少なくとも3回行ったとき、得られる共重合体の重量平均分子量がそれぞれ、ゲルパーミエーションクロマトグラフィーによるポリエチレングリコール換算で、10000~300000の範囲内であり、得られる共重合体の重量平均分子量の変動係数CVが、0.04以下である、請求項1から7までのいずれかに記載の製造方法。
- 重量平均分子量が、ゲルパーミエーションクロマトグラフィーによるポリエチレングリコール換算で、10000~300000であり、該重量平均分子量の変動係数CVが、0.04以下であり、
一般式(1)で表される不飽和ポリアルキレングリコールエーテル系単量体(a)由来の構造単位(I)50重量%~99重量%と、一般式(2)で表される不飽和モノカルボン酸系単量体(b)由来の構造単位(II)1重量%~50重量%と、該単量体(a)および/または該単量体(b)と共重合可能な単量体(c)由来の構造単位(III)0重量%~49重量%(ただし、構造単位(I)、構造単位(II)、および構造単位(III)の合計は100重量%である)とを有する共重合体。
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