WO2014069571A1 - ビニルアミン単位含有重合体溶液の製造方法 - Google Patents
ビニルアミン単位含有重合体溶液の製造方法 Download PDFInfo
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- WO2014069571A1 WO2014069571A1 PCT/JP2013/079554 JP2013079554W WO2014069571A1 WO 2014069571 A1 WO2014069571 A1 WO 2014069571A1 JP 2013079554 W JP2013079554 W JP 2013079554W WO 2014069571 A1 WO2014069571 A1 WO 2014069571A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
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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
- C08F26/00—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/02—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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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
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the present invention relates to a method for producing a vinylamine unit-containing polymer solution. More specifically, the present invention relates to a high-molecular-weight vinylamine unit-containing polymer useful as a papermaking agent in the paper processing industry in addition to a flocculant in the water treatment field, particularly wastewater treatment. The present invention relates to a method for producing a combined solution.
- the vinylamine unit-containing polymer may be simply abbreviated as polyvinylamine.
- Polyvinylamine is a useful substance that is widely used as a flocculant, a papermaking agent, a fiber treatment agent, a paint additive, and the like.
- a flocculant in wastewater treatment or a papermaking agent in the paper industry, high molecular weight polyvinylamine is considered effective.
- polyvinylamine is a polymer or copolymer of N-vinylcarboxylic acid amide (hereinafter collectively referred to as a (co) polymer) in the presence of an acid or an alkali, in whole or in part. It is obtained by hydrolysis.
- high molecular weight polyvinylamine is difficult to handle because it becomes extremely high viscosity when it is made into an aqueous solution.
- it is easy to handle if diluted, but there are problems such as increased costs in production and transportation.
- N-vinylcarboxylic acid amide polymer powder is subjected to alkaline hydrolysis to form an aqueous solution.
- the N-vinylcarboxylic acid amide (co) polymer has a reduced viscosity of 9 or more.
- a molecular weight product is preferred (Patent Document 1).
- the resulting aqueous solution has a high viscosity and is extremely difficult to handle.
- an aqueous solution stationary adiabatic polymerization method has been proposed as a polymerization method of N-vinylcarboxylic acid amide (Patent Document 2).
- this proposal does not explain how to convert to polyvinylamine and its functionality.
- N-vinylcarboxylic acid amide (co) polymer it is industrially advantageous to hydrolyze the N-vinylcarboxylic acid amide (co) polymer to polyvinylamine under alkaline conditions.
- acid hydrolysis all equipment piping related to production, transportation, storage and use is required to have corrosion resistance, whereas in alkaline conditions, ordinary steel or stainless steel equipment piping may be used. Is possible.
- a solution is advantageous as a product form. That is, in the production of a powder product, a powder drying step is essential. However, when polyvinylamine is heated at a high temperature, the product may deteriorate and the solubility of the product may deteriorate. Such deterioration is a very important problem particularly in papermaking chemicals that require high solubility. In addition, powders require a facility for melting when used.
- the product form is preferably alkaline and in a uniform solution state, and this is already known (Patent Document 1).
- Patent Document 1 no countermeasure has been proposed to cope with the fact that an aqueous solution of high molecular weight polyvinylamine becomes extremely viscous.
- the present inventor has found that the performance of papermaking chemicals, especially the yield filtering agent, is different in performance even if the molecular weight distribution is different even with the same reduced viscosity, the molecular weight distribution is
- the polyvinylformamide produced by the adiabatic polymerization method varies depending on the polymerization method, and exhibits excellent performance even when the molecular weight distribution is wide and the average molecular weight is relatively low.
- the present inventors have found that a high-performance polyvinylamine aqueous solution can be made for drugs and the like, and have reached the present invention.
- the gist of the present invention is to produce a polymer containing an N-vinylcarboxylic acid amide monomer unit and having a weight average molecular weight Mw / number average molecular weight Mn of 5 or more by an aqueous solution adiabatic polymerization method. Then, the polymer is hydrolyzed in an aqueous solvent in the presence of an alkali and an antigelling agent, and the method lies in a method for producing a vinylamine unit-containing polymer solution.
- a polyvinylamine solution having high performance and good handleability can be produced industrially and efficiently.
- Such a high molecular weight polyvinylamine solution is extremely useful because it can be widely applied in various fields including papermaking chemicals in the paper industry.
- the (co) polymer powder handled in the middle of the production method of the present invention can be stored for a long period of time and can be handled easily, and is dissolved in an alkaline aqueous solution as it is and heated to obtain a polyvinylamine aqueous solution. Obtainable. Therefore, the polyvinylamine aqueous solution can be produced when necessary at the place of use, and transportation costs and storage costs can be reduced, which is economically advantageous. Moreover, since it is not necessary to preserve
- N-vinylcarboxylic amide (co) polymer The N-vinylcarboxylic acid amide used in the present invention is represented by the general formula: CH 2 ⁇ CH—NHCOR (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
- R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- N-vinylformamide (R H)
- N-vinylcarboxylic acid amide can be copolymerized with any monomer having an ethylenically unsaturated bond, if necessary.
- monomers that can be copolymerized include (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, (meth) acrylonitrile, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N -Dialkyl (meth) acrylamide, dialkylaminoethyl (meth) acrylamide and salts or quaternized compounds thereof, dialkylaminopropyl (meth) acrylamide and salts or quaternized compounds thereof, diacetone acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam And vinyl acetate.
- the content ratio of N-vinylcarboxylic acid amide in the monomer composition is usually 5 mol% or more, preferably 10 mol% or more, more preferably 50 mol% or more, although it depends on the target (co) polymer. 70 to 100 mol% is preferred.
- said monomer composition is reflected as a composition of a (co) polymer.
- an aqueous solution adiabatic polymerization method is selected.
- the stationary adiabatic polymerization method is a method of polymerizing in a reaction tank that does not have a device for removing heat of reaction and a stirring device during polymerization.
- the temperature in the system rises because it generates heat but does not remove heat. Therefore, if the monomer concentration is too high, it boils, and if it is too low, the production efficiency is poor.
- the monomer concentration is usually 10 to 50% by mass, preferably 20 to 40% by mass, and more preferably 25 to 35% by mass.
- the polymerization initiation temperature is preferably low in order to increase the polymerization concentration without boiling, but if it is too low, it will freeze, so it is usually from -10 to + 20 ° C, preferably from -10 to + 10 ° C. Selected.
- the aqueous solution polymerization is performed with a radical polymerization initiator.
- a radical polymerization initiator a normal redox initiator, azo initiator, peroxide and a combination thereof can be used. These initiators may be either water-soluble or oil-soluble. However, when using an oil-soluble initiator, it is necessary to add it by dissolving it in a water-soluble solvent.
- water-soluble azo initiators examples include 2,2′-azobis (amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] And hydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like.
- oil-soluble azo initiators examples include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile), Examples include 2,2′-azobis (2-methylpropionate) and 2,2′-azobis (4-methoxy-2,4dimethyl) valeronitrile.
- redox initiators include combinations of ammonium peroxodisulfate and sodium sulfite, sodium bisulfite, trimethylamine, tetramethylethylenediamine, etc., t-butyl hydroperoxide and sodium sulfite, sodium bisulfite, ferrous sulfate And the like.
- peroxides examples include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy-2-ethylhexanoate, etc. Can be mentioned.
- Most preferred among these initiators is a combination of a redox initiator that initiates polymerization at a low temperature and a water-soluble azo initiator that starts at a relatively high temperature.
- a redox initiator t-butyl hydroperoxide is used.
- 2,2′-azobis (2-amidinopropane) dihydrochloride as a water-soluble azo initiator in combination with sodium sulfite, sodium hydrogen sulfite and ferrous sulfate.
- the amount of the polymerization initiator used is usually 100 to 10,000 ppm, preferably 500 to 5000 ppm in the case of an azo initiator, and usually 10 to 700 ppm, preferably 30 to 30 in the case of a redox initiator relative to the monomer. 600 ppm. If the amount of the polymerization initiator used is too small, a sufficient polymerization rate cannot be obtained, and if it is too large, the polymerization rate increases but the molecular weight decreases, which is not preferable.
- ⁇ sp / C is Usually, it is 2 to 9, preferably 2 to 8.
- the adjustment may be performed using the reaction temperature, the type and amount of the initiator, and further using a known chain transfer agent.
- chain transfer agent examples include alcohols such as isopropyl alcohol and allyl alcohol, mercaptans such as thioglycolic acid and thioglycerol, and phosphites such as sodium hypophosphite.
- the molecular weight distribution is represented by the ratio Mw / Mn of the weight average molecular weight and the number average molecular weight.
- Mw / Mn can be calculated by, for example, size exclusion chromatography.
- GPC gel permeation chromatography
- GFC gel filtration chromatography
- the Mw / Mn value of the polymer produced by the present invention measured by these methods is 5 or more.
- a chain transfer agent may be used.
- the chain transfer agent is not particularly limited unless Mw / Mn is less than 5.
- the aqueous solution adiabatic polymerization method is not particularly limited, but may be performed in the presence of an inorganic salt. Specifically, for example, it is performed as follows. That is, water, inorganic salt, monomer, etc. are mixed to prepare a monomer preparation liquid (uniform monomer aqueous solution) adjusted to the polymerization start temperature, and this is injected into an adiabatic reaction tank. The body preparation solution is aerated with nitrogen to remove dissolved oxygen, and an initiator is added thereto and mixed to start the polymerization reaction.
- a monomer preparation liquid uniform monomer aqueous solution
- the body preparation solution is aerated with nitrogen to remove dissolved oxygen, and an initiator is added thereto and mixed to start the polymerization reaction.
- the inorganic salt is not particularly limited as long as it is water-soluble, but a metal halide is preferable from the viewpoints of handleability and cost.
- the metal halide include alkali metal and alkaline earth metal halides, specifically sodium chloride, potassium chloride, calcium chloride, potassium bromide, sodium bromide and the like.
- preferred examples of the metal halide include chlorides. Specifically, sodium chloride, potassium chloride, calcium chloride and the like are preferred because they are inexpensive, but sodium chloride is more preferred.
- the concentration of the inorganic salt is 7% by mass or more with respect to water in the homogeneous aqueous solution containing the monomer and is equal to or less than the saturated dissolution concentration at the polymerization initiation temperature, preferably 80% or less of the saturated dissolution concentration.
- the conversion rate of N-vinylcarboxylic acid amide is usually 90% or more, preferably 95% or more, more preferably 98% or more, and particularly preferably 99% or more.
- the obtained (co) polymer contains water according to the polymerization method. Although it may be diluted as it is to make an aqueous solution and hydrolyzed, in the present invention, it is preferably dried and powdered by any method. By making it dry powder, it can be stored and transported stably with good handleability. Further, when it is dissolved in an aqueous solvent in the subsequent modification step, since the specific surface area is large, it can be uniformly dissolved in a short time.
- a gel-like polymer mass is obtained, so that powder can be obtained by pulverizing and drying the gel.
- a massive aqueous gel is pulverized after cutting into particles.
- the average particle size at the time of pulverization is usually 5 cm or less, preferably 2 cm or less, more preferably 1 cm or less.
- Various known methods can be adopted as the pulverization method, and there are a method of cutting the gel with a cutter or the like, and a method of cutting the gel with a meat chopper or the like.
- the hole diameter of the die of the meat chopper is usually 5 cm or less, preferably 2 cm or less, more preferably 1 cm or less, and particularly preferably 1 to 7 mm.
- the obtained granular material is usually dried at 50 to 140 ° C., preferably 60 to 130 ° C., more preferably 70 to 120 ° C. If the drying temperature is too low, the drying efficiency is poor, and if the drying temperature is too high, the quality of the (co) polymer may be deteriorated.
- the volatile content of the polymer powder after drying is usually 0.1 to 12% by mass from the viewpoint of easy handling. If the amount of volatile components is large, the powder tends to stick, and the particles may be soft and difficult to grind. On the other hand, if the amount of volatile components is reduced too much, an excessive amount of heat and time are required for drying, and the (co) polymer may be deteriorated due to overheating.
- the volatile matter here is mainly moisture.
- the particle size of the (co) polymer powder is usually 4 mesh pass to 500 mesh on, preferably 80% or more, preferably 90% or more in the range of 10 mesh pass to 100 mesh on. Good.
- An auxiliary agent may be used to suppress adhesion between particles during crushing and fine granulation.
- an auxiliary agent polyalkylene glycols, various oils such as silicone oil, surfactants and the like are used.
- the auxiliary agent may be applied to the surface of the bulk aqueous gel before pulverization, added together with the aqueous gel in a pulverizer, or mixed with the granular gel after pulverization.
- the auxiliary may be present in advance in the polymerization reaction water system. It is also useful to add a salt at the time of polymerization as shown in Patent Document 2. Thereby, the adhesion at the time of crushing the gel is suppressed, and the processing becomes easy.
- the aqueous gel is too soft or too sticky when crushing or making fine particles, it will adhere without being cut by a cutter. Moreover, even if it can cut, the cutting speed will fall. However, if an inorganic salt is present in the polymerization system in accordance with a preferred embodiment of the method of the present invention, the resulting aqueous (co) polymer gel has a suitable hardness and can be easily cut into fine particles.
- the aqueous gel of the resulting polymer may become soft, and it may not be possible to process the particles by pulverization of the gel.
- an inorganic salt is present according to a preferred embodiment of the method of the present invention, even when a (co) polymer having a lower molecular weight than usual is produced, the aqueous gel of the resulting polymer has a hardness that is easy to handle.
- the atomization process can be performed with a normal apparatus.
- N-vinylcarboxylic acid amide (co) polymer having a broad molecular weight distribution two or more kinds of N-vinylcarboxylic acid amide (co) polymers having different reduced viscosities may be mixed.
- the reduced viscosity of the N-vinylcarboxylic acid amide (co) polymer after mixing is preferably 2 to 9.
- Hydrolysis is performed in the presence of alkali. Hydrolysis is possible under both acid and base conditions, but alkali is less susceptible to equipment corrosion.
- the type of alkali is not limited as long as it can hydrolyze the N-vinylcarboxylic acid amide (co) polymer. Specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide Etc. are exemplified. These alkalis may be used alone or as a mixture.
- the amount of alkali varies depending on the desired hydrolysis rate, but is usually 10 to 1 times equivalent to the vinylamine unit in the target polyvinylamine. In the case where a substance that is more easily hydrolyzed than the N-vinylamide group coexists in the hydrolysis reaction system, it is necessary to use an excessive amount to offset it.
- the order of addition of necessary components in the hydrolysis reaction is preferably such that the total amount of (co) polymer powder is added to the aqueous alkali solution and dissolved.
- the reason is as follows. That is, it is possible to dissolve or add the (co) polymer powder later, but when it is desired to dissolve the (co) polymer having the target molecular weight at a high concentration, the viscosity of the aqueous solution is low. This is because it is extremely large, and when alkali is added later, it takes a long time for uniform mixing, and insoluble matters are generated.
- the aqueous solvent is basically water, but depending on the copolymer composition, a mixed solvent containing another organic solvent may be used to adjust the solubility of the polymer.
- a mixed solvent containing another organic solvent include methanol, ethanol, isopropanol, acetone, acetonitrile and the like.
- neutral salts may be contained in the solvent.
- the salts include chlorides such as sodium chloride, potassium chloride, ammonium chloride, calcium chloride, and zinc chloride, nitrates such as sodium nitrate and potassium nitrate, sulfates such as sodium sulfate and ammonium sulfate, sodium phosphate, and ammonium phosphate.
- Organic acid salts such as phosphate, sodium acetate, sodium formate and the like can be mentioned. These salts have the effect of adjusting the solution viscosity.
- the hydrolysis is carried out in the presence of an antigelling agent.
- an antigelling agent any known compound can be used as the anti-gelling agent, in the present invention, those which are stable in alkali and have an aldehyde scavenging ability are preferably used.
- Specific examples of such anti-gelling agents include dithionite, sulfite, bisulfite, disulfite, Rongalite (sulfoxylate formaldehyde adduct), thiourea dioxide, sodium borohydride and the like. Illustrated.
- a salt the kind can be arbitrarily selected, and examples thereof include alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium, magnesium and zinc, and ammonium salts. Any one or more of these anti-gelling agents can be used as a mixture.
- sulfite, bisulfite, and disulfite have a slightly weaker aldehyde scavenging ability than other anti-gelling agents, so it is necessary to increase the amount of addition. Therefore, in terms of performance, dithionite, Rongalite, thiourea dioxide, and sodium borohydride are particularly excellent. Of these, dithionite is somewhat unstable in air and requires care in handling. In addition, sodium borohydride needs to be noted that hydrogen bubbles may be generated during reaction and during product storage.
- the addition amount of the gelling inhibitor depends on the amount of residual monomer in the (co) polymer, but is usually 0.01 to 20% by mass, preferably 0.1 to 10% by mass with respect to the (co) polymer. %, More preferably 0.2 to 5% by mass.
- the anti-gelling agent is previously dissolved in an aqueous solvent before the (co) polymer powder is dissolved. It is of course possible to dissolve or add later, but since the (co) polymer solution has a very high viscosity, it is difficult to uniformly mix it when an antigelling agent is added later. Further, the gelation inhibitor may be dissolved simultaneously with the (co) polymer powder. Furthermore, since the said antigelling agent is marketed normally as a powder, it can also be mix
- the concentration of the (co) polymer in the aqueous solvent needs to be appropriately selected in order to perform uniform hydrolysis.
- the (co) polymer concentration is determined based on a balance between the ability of the dissolution apparatus, the production efficiency, the economics such as transportation costs, and the like.
- the concentration is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more.
- the concentration is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.
- the type of the dissolution apparatus is not particularly limited, but it is essential that the high viscosity liquid can be effectively stirred.
- solid-liquid mixing apparatuses such as a stirring tank type, a pump type, an extruder type, and a kneading type can be used.
- a helical ribbon blade suitable for stirring a highly viscous liquid can be used as the stirring blade.
- the hydrolysis conditions vary depending on the (co) polymer concentration and alkali concentration, but are usually 30 to 180 ° C, preferably 40 to 140 ° C, and more preferably 50 to 100 ° C.
- the heating time may be determined according to a desired hydrolysis rate, but there is a risk of promoting deterioration when heated at a high temperature for a long time. Therefore, the heating time is usually within 48 hours, preferably within 24 hours, and more preferably within 12 hours.
- the apparatus used for the hydrolysis is not particularly limited as long as the (co) polymer solution can be heated.
- equipment suitable for stirring high viscosity liquids such as a stirring tank type, pump type, extruder type, kneading type, etc. is used, and a heating method using a heat medium such as hot water, steam, or hot oil is adopted from the outside. Is done.
- the reaction may be continued in an apparatus in which the (co) polymer is dissolved.
- the reaction temperature is increased, hydrolysis is possible even with a very short heating time. In this case, the selection of equipment becomes wider, for example, multi-tube type, plate type, wet wall type, thin film type, etc. Heating methods using heat exchangers, microwaves, infrared rays and the like can be mentioned.
- the heating device as described above, it is possible to perform a hydrolysis reaction at a place where polyvinylamine is used, for example, at a paper mill or a wastewater treatment facility. That is, it is possible to carry in (co) polymer as a powder, prepare a solution, hydrolyze it when necessary, and introduce it directly into equipment used, that is, a papermaking apparatus or a wastewater treatment apparatus.
- the production at the place of use of polyvinylamine does not require large facilities for production and storage of dilute polyvinylamine aqueous solution. Further, since it can be transported as a (co) polymer powder to the place of use, there is no need to transport a dilute solution, and the transportation cost can be reduced, which is economically advantageous.
- the aqueous polyvinylamine solution thus prepared may be further diluted, adjusted in pH, added with other chemicals, etc. immediately before being introduced into the equipment to be used.
- concentration of the vinylamine unit containing (co) polymer solution obtained by the said hydrolysis is suitably set according to the intended purpose.
- aqueous polyvinylamine aqueous solution When hydrolysis is completed, an aqueous polyvinylamine solution is obtained. Depending on the concentration during hydrolysis, an aqueous solution of 1 to 30% by mass is obtained. The concentration may be adjusted to facilitate handling. The preferred concentration depends on the molecular weight of the (co) polymer, but is 2 to 25% by mass, more preferably 3 to 30% by mass. When the concentration is lower than this, the liquid viscosity is lowered and the handleability is improved regardless of the molecular weight distribution, but the cost for transportation and the like increases. If it is higher than this, the liquid viscosity becomes too high regardless of the molecular weight distribution, although it depends on the molecular weight of the polymer.
- Polyvinylamine can be applied to various fields, and high molecular weight polyvinylamine is said to be effective particularly when used as a papermaking chemical in the paper industry, particularly as a yield filtration agent or a flocculant in wastewater treatment.
- performance equivalent to or higher can be obtained without using polyvinylamine having a reduced viscosity of 9 or more which has been conventionally recommended.
- handleability as an aqueous solution is also good.
- a high molecular weight polyvinylamine solution product can be industrially efficiently produced under alkaline conditions.
- Alkaline conditions are advantageous because they are less constrained by equipment in the manufacture, transport, storage and use of products.
- the hydrolysis reaction can be performed in a paper mill or a wastewater treatment facility, which is advantageous in terms of economy and quality.
- the (co) polymer sample was dissolved in 1N saline to a concentration of 0.1 g / dl pure, and the flow-down time was measured at 25 ° C. using an Ostwald viscometer. Similarly, the flow time of 1N saline was measured, and the reduced viscosity was determined by the following formula 1.
- the (co) polymer powder was extracted with methanol water and the residual monomer was analyzed using liquid chromatography.
- main impurities N-vinyl carboxylic acid amide and water adducts of N-vinyl carboxylic acid amide were detected, and the total amount of these was calculated in terms of N-vinyl carboxylic acid amide, and the amount of residual monomer was obtained separately. was corrected to calculate the conversion rate.
- the (co) polymer powder was heated at 105 ° C. for 90 minutes, and the decrease was determined by the gravimetric method.
- aqueous solution viscosity The temperature of the aqueous polymer solution was 25 ° C., Brookfield viscometer, 6 rpm, rotor No. The measurement was performed under the condition of 4. The viscosity was expressed as mPa ⁇ s.
- Example 1 Synthesis and Performance Evaluation of Polymer A; Aqueous Solution Adiabatic Polymerization Method
- polyethylene glycol average molecular weight 20000
- N-vinylformamide purity 99% by weight
- This monomer preparation was cooled to 0 ° C., then transferred to an adiabatic reaction vessel equipped with a thermometer and subjected to nitrogen aeration for 15 minutes, followed by 2,2′-azobis (2-amidinopropane) dihydrochloride (product) Name: Wako Pure Chemical Industries “V-50”) 1500 ppm (compared to monomer) and t-butyl hydroperoxide (trade name: “Perbutyl H-69” manufactured by NOF Corporation) 200 ppm (compared to monomer) Polymerization was started by adding as a 10% by mass aqueous solution and then adding 600 ppm ferrous sulfate heptahydrate (based on monomer) as a 10% by mass aqueous solution.
- N-vinylformamide gel polymer gel is cut into 3 cm square, the cut gel piece is treated with a meat chopper with a die hole diameter of 4.8 mm, and the gel piece is reduced to 5 mm square or less did.
- the obtained gel granules maintained a fine-grained shape and had good handleability.
- the granular material was dried at 80 ° C. for 2 hours, and the dried granular material was pulverized by a Willet type pulverizer to obtain a powder (particle size: 10 mesh pass to 100 mesh on: 95% or more).
- the reduced viscosity was 7.2 [dl / g]
- the polymerization conversion was 99.7%
- the volatile content was 3.2% by mass.
- Mw / Mn measured by GPC method was 11.58.
- this polymer as the polymer A the following physical properties and performance evaluation of the polymer solution were carried out.
- Example 2 Synthesis and Performance Evaluation of Polymer B; Aqueous Solution Adiabatic Polymerization Method
- Polymerization was carried out in the same manner as for polymer A except that the amount of 2,2′-azobis (2-amidinopropane) dihydrochloride was increased to 2000 ppm to obtain an N-vinylformamide polymer powder having a reduced viscosity of 5.8 dl / g. .
- the polymerization conversion was 99.8% and the volatile content was 4.5% by mass.
- Mw / Mn measured by GPC method was 6.5.
- the physical properties and performance evaluation of the following polymer solutions were carried out.
- Example 3 Preparation of polymer D and performance evaluation
- the said polymer C and the polymer A were mixed so that it might become 70 mass% / 30 mass%, and it was set as the polymer D.
- the reduced viscosity was 6.4 dl / g
- the polymerization conversion was 99.8%
- the volatile content was 4.5% by mass.
- Mw / Mn measured by GPC method was 9.1.
- the polymer D was subjected to physical properties and performance evaluation of the following polymer solutions.
- “Comparative Example 1” (Synthesis and performance evaluation of polymer E; photopolymerization method) 333.3 g (purity 99%) of N-vinylformamide as a monomer, 0.11 g of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide as an initiator, 5.5 g of ammonium chloride, “Sanisol B50” (Kao chloride benza manufactured by Kao) Prepare a monomer solution by uniformly dissolving 0.55 g of a ruthenium-based surfactant (purity 50%), 0.055 g of “AF108” (surfactant manufactured by Toho Chemical Co., Ltd.), and 210.5 g of demineralized water. Aerated to remove dissolved oxygen.
- a polyethylene terephthalate film (base film 12 ⁇ m thickness, PVDC coat 4 ⁇ m thickness) is laid on the bottom surface of a stainless steel tray-like container (bottom surface 235 mm ⁇ 235 mm), the monomer solution is put here, and the top is covered with a polyethylene terephthalate film did.
- the fluorescent chemical lamp was irradiated so as to have an intensity of 3 W / m 2 on the irradiated surface.
- 10 ° C. cold water was sprayed on the stainless steel surface of the container to remove the heat of polymerization.
- the temperature which was 15 ° C. before irradiation, reached a maximum of 42 ° C. after 90 minutes. 120 minutes after the start of irradiation, the irradiation intensity was increased to 6.5 W / m 2 and polymerization was continued for 60 minutes.
- a colorless and transparent gel which is an N-vinylformamide polymer was obtained.
- the gel was pulverized with a meat chopper to make particles of about 4 to 5 mm, and then dried for 2 hours with an air dryer at 80 ° C. Thereafter, it was pulverized again with a rotary pulverizer having a 1 mm ⁇ screen to obtain an N-vinylformamide polymer powder.
- the amount of volatile components was 4.7% by mass, and the polymerization conversion rate was 98.7%.
- the reduced viscosity was 11.6 dl / g. Mw / Mn measured by GPC method was 4.6. Using this product as polymer E, physical properties and performance evaluation of the following polymer solutions were carried out.
- “Comparative Example 2” (Synthesis and performance evaluation of polymer F) Polymerization was carried out in the same manner as for Polymer B except that the amount of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide was increased to 0.55 g to obtain an N-vinylformamide polymer powder having a reduced viscosity of 8.3 dl / g. . The polymerization conversion was 99.0% and the volatile content was 4% by mass. Mw / Mn measured by GPC method was 4.2. Using this product as a polymer F, the physical properties and performance of the following polymer solutions were evaluated.
- polyvinylamine obtained by hydrolyzing polymers A, B, D, and E exhibits substantially the same drainage and squeezability, but polymer E has a high solution viscosity and is inferior in handleability.
- Polyvinylamine obtained by hydrolyzing polymer F has substantially the same handleability as polymers A, B, and D, but is inferior in terms of performance (drainage and squeezability).
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Abstract
Description
本発明で使用されるN-ビニルカルボン酸アミドは、一般式:CH2=CH-NHCOR(式中、Rは水素原子または炭素数1~6のアルキル基を表す)で示される。具体的にはN-ビニルホルムアミド(R=H)やN-ビニルアセトアミド(R=CH3)、その他、N-ビニルプロピオン酸アミド(R=C2H5)、N-ビニル酪酸アミド(R=C3H7)等が例示されるが、ポリビニルアミンへの誘導のし易さからN-ビニルホルムアミドが好ましい。
広い分子量分布を保ちつつ、還元粘度を前記の値に保つために、連鎖移動剤を用いてもよい。連鎖移動剤はMw/Mnを5より小さくしなければ特に制約は無い。
次いで、N-ビニルカルボン酸アミド(共)重合体の一部または全部を加水分解し、ポリビニルアミンに転換する。
加水分解が終了するとポリビニルアミンの水溶液となる。加水分解時の濃度により異なるが、1~30質量%の水溶液が得られる。濃度は取り扱い性がよいように調節してもよい。好ましい濃度は(共)重合体の分子量にもよるが2~25質量%より好ましくは3~30質量%である。これより低濃度の場合、分子量分布にかかわらず、液粘性が低くなり取り扱い性は良くなるが、運搬等のコストが増大する。これより高い場合、重合体の分子量にもよるが分子量分布にかかわらず液粘性が高くなりすぎる。
ポリビニルアミンは各種分野に適用でき、特に製紙工業での抄紙薬剤、中でも歩留まり濾水剤、廃水処理での凝集剤などとして使用する場合には、高分子量のポリビニルアミンが有効であるとされているが、本発明によれば、従来より推奨されていた還元粘度9以上のポリビニルアミンを使用せずとも、同等以上の性能が得られる。さらに水溶液としての取り扱い性も良好である。
(共)重合体サンプルを1Nの食塩水中に、純分0.1g/dlの濃度に溶解し、25℃において、オストワルド粘度計を使用して流下時間を測定した。同様に、1N食塩水の流下時間を測定し、下記の式1によって還元粘度を求めた。
還元粘度 ηsp/C = (t-t0)/t0/0.1 [dl/g]・・・・(式1)
t:サンプル溶液の流下時間(秒)
t0:1N食塩水の流下時間(秒)
(共)重合体粉末をメタノール水で抽出し、残存単量体を液体クロマトグラフィーを使用して分析した。主たる不純物として、N-ビニルカルボン酸アミドと、N-ビニルカルボン酸アミドの水付加体が検出され、これらの合計をN-ビニルカルボン酸アミド換算で求めて残存モノマー量とし、別途求めた揮発分量を補正して転化率を算出した。
(共)重合体粉末を105℃で90分加熱し、減少分を重量法で求めた。
重合体水溶液の温度を25℃とし、ブルックフィールド粘度計、6rpm、ローターNo.4の条件にて測定した。なお、粘度は、mPa・sと表記した。
(重合体Aの合成及び性能評価;水溶液静置断熱重合法)
脱イオン水70質量部に対しポリエチレングリコール(平均分子量20000) 0.3質量部を溶解し、次いで、N-ビニルホルムアミド(純度99重量%)30質量部を混合した。更に、酢酸ソーダ0.1質量部を添加後リン酸により単量体水溶液がpH=6.3となるように調整し、単量体調製液を得た。
(重合体Bの合成及び性能評価;水溶液静置断熱重合法)
2,2’-アゾビス(2-アミジノプロパン)二塩酸塩を2000ppmに増量したほかは重合体Aと同様方法で重合を行い還元粘度5.8dl/gのN-ビニルホルムアミド重合体粉末を得た。重合転化率は99.8%、揮発分量は4.5質量%であった。GPC法により測定したMw/Mnは6.5であった。この製品を重合体Bとして、以下の重合体溶液の物性と性能評価を実施した。
2,2’-アゾビス(2-アミジノプロパン)二塩酸塩を2500ppmに増量したほかは重合体Aと同様方法で重合を行い還元粘度3.9dl/gのN-ビニルホルムアミド重合体粉末を得た。重合転化率は99.8%、揮発分量は4.5質量%であった。GPC法により測定したMw/Mnは5.1であった。この製品を重合体Cとした。
(重合体Dの調製及び性能評価)
前記重合体Cと重合体Aを70質量%/30質量%となるよう混合し、重合体Dとした。重合体Dを分析したところ、還元粘度6.4dl/g、重合転化率は99.8%、揮発分量は4.5質量%であった。GPC法により測定したMw/Mnは9.1であった。この重合体Dを以下の重合体溶液の物性と性能評価を実施した。
(重合体Eの合成及び性能評価;光重合法)
モノマーとしてN-ビニルホルムアミド333.3g(純度99%)、開始剤としてジフェニル(2,4,6-トリメチルベンゾイル)ホスフィンオキサイド0.11g、塩化アンモニウム5.5g、「サニゾールB50」(花王製塩化ベンザルコニウム系界面活性剤、純度50%)0.55g、「AF108」(東邦化学製界面活性剤)0.055g、脱塩水210.5gを均一に溶解してモノマー溶液を調製し、窒素ガスを通気して溶存酸素を除去した。
(重合体Fの合成及び性能評価)
ジフェニル(2,4,6-トリメチルベンゾイル)ホスフィンオキサイドを0.55gに増量したほかは重合体Bと同様方法で重合を行い還元粘度8.3dl/gのN-ビニルホルムアミド重合体粉末を得た。重合転化率は99.0%、揮発分量は4質量%であった。GPC法により測定したMw/Mnは4.2であった。この製品を重合体Fとして、以下の重合体溶液の物性と性能評価を実施した。
攪拌機を有するガラス製セパラブルフラスコに、脱塩水275.2gを入れ、水酸化ナトリウム8.45g、ゲル化防止剤として亜二チオン酸ナトリウム0.75gを溶解し、ここに前記N-ビニルカルボン酸アミド重合体純分15gを撹拌下少しづつ加え、室温で1時間攪拌後、50℃に昇温した。2時間後、更に、80℃に昇温し、80℃で2時間保持して加水分解を行った。冷却後、内容物のポリビニルアミン溶液を取り出した。ポリビニルアミンの水溶液粘度を測定し、表1に示す。
段ボールを水に浸した後ビーターを使用して20分叩解して濃度を調節し、カナダ標準濾水量(CFS)=90、濃度1%、pH6.91の試験用スラリーを得た。そして、濾水性は、次のようにして評価した。すなわち、スラリー500mlに濾水剤として前記ポリビニルアミン溶液を重合体純分として200ppm(対段ボール)を添加し、パドル翼で900rpmで20秒撹拌、その後、ダイナミックドレネージジャー試験機(熊谷理機工業社製)にて10秒後の濾水量を測定した。一方、同一スラリーを使用して角型シートマシンを使用して手抄きにて抄紙、紙葉を濾布に挟み、0.4MPaプレス機で5分、更に、0.4MPaで2分プレス、その状態で含水率を調べ搾水性の目安とした。結果を表1に示す。
Claims (12)
- N-ビニルカルボン酸アミド単量体単位を含有する、重量平均分子量Mw/数平均分子量Mnの値が5以上である重合体を水溶液静置断熱重合法にて製造した後、前記重合体をアルカリ及びゲル化防止剤の存在下に水性溶媒中で加水分解を行うことを特徴とする、ビニルアミン単位含有重合体溶液の製造方法。
- ビニルアミン単位含有重合体溶液が製紙用内添薬剤である請求項1に記載の製造方法。
- 重合体中のN-ビニルカルボン酸アミド単量体単位が50モル%以上である請求項1又は2に記載の製造方法。
- N-ビニルカルボン酸アミド単量体単位がN-ビニルホルムアミド単量体単位である請求項1~3の何れかに記載の製造方法。
- ゲル化防止剤が、亜二チオン酸塩、亜硫酸塩、重亜硫酸塩、二亜硫酸塩、ロンガリット、二酸化チオ尿素、水素化ホウ素ナトリウムの群から選ばれる少なくとも一つである請求項1~4の何れかに記載の製造方法。
- ビニルアミン単位含有重合体溶液が製紙用歩留まり濾水剤である請求項1に記載の製造方法。
- 重合体の1N食塩水中0.1g/dlの還元粘度が2~9である。請求項1~6の何れかに記載の製造方法。
- 加水分解を行う際の水性溶媒中の重合体濃度が3質量%以上である請求項1~7の何れかに記載の製造方法。
- 水性溶媒中の重合体濃度が3質量%以上である請求項1~7の何れかに記載の製造方法。
- 水溶液静置断熱重合にてN-ビニルカルボン酸アミド単量体単位を含有する重合体を製造した後、乾燥粉末化して揮発分が0.1~12質量%の重合体粉末を得、次いで、得られた前記粉末をアルカリ及びゲル化防止剤の存在下に水性溶媒中で加水分解を行う、請求項1に記載の重合体溶液の製造方法。
- 得られた重合体粉末を重合体溶液の使用場所に搬送し、当該使用場所において、重合体粉末をアルカリ及びゲル化防止剤の存在下に水性溶媒中で加水分解を行う、請求項10に記載の重合体溶液の製造方法。
- 重合体が還元粘度の異なる2種以上のN-ビニルカルボン酸アミド重合体の混合物である請求項1の方法。
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JP2006257287A (ja) * | 2005-03-17 | 2006-09-28 | Daiyanitorikkusu Kk | 水溶性ビニルアミン重合体の製造方法 |
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JP2004027015A (ja) | 2002-06-25 | 2004-01-29 | Daiyanitorikkusu Kk | ポリビニルアミンの製造方法 |
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