WO2015068806A1 - ビニルアミン(共)重合体の製造方法 - Google Patents
ビニルアミン(共)重合体の製造方法 Download PDFInfo
- Publication number
- WO2015068806A1 WO2015068806A1 PCT/JP2014/079590 JP2014079590W WO2015068806A1 WO 2015068806 A1 WO2015068806 A1 WO 2015068806A1 JP 2014079590 W JP2014079590 W JP 2014079590W WO 2015068806 A1 WO2015068806 A1 WO 2015068806A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- acid amide
- vinylcarboxylic acid
- mass
- vinylamine
- Prior art date
Links
Classifications
-
- 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
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—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
-
- 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
-
- 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 vinylamine (co) polymer.
- Vinylamine (co) polymers are useful substances that are widely used as flocculants, papermaking agents, fiber treatment agents, paint additives, and the like. Depending on the application, polymers of various molecular weights are required over a wide range from high molecular weight polymers having a molecular weight of 4 million or more to low molecular weight polymers having a molecular weight of 100,000 or less.
- the “(co) polymer” refers to a polymer or a copolymer.
- N-vinylcarboxylic acid amide (co) polymers are hydrolyzed in the presence of acid or base to give vinylamine (co) polymers.
- a method for producing a coalescence is generally performed.
- a method for producing an N-vinylcarboxylic acid amide (co) polymer a method such as a reverse phase suspension polymerization method, an emulsion polymerization method, a photopolymerization method, an aqueous solution standing adiabatic polymerization method, or an aqueous solution dropping polymerization method is used. I came.
- the photopolymerization method and the aqueous solution stationary adiabatic polymerization method are simple, and have an advantage that polymers having various molecular weights can be prepared by appropriately selecting the polymerization conditions.
- N-vinylcarboxylic acid amide (co) polymers are used in a wide range of molecular weights from high molecular weight polymers to low molecular weight polymers depending on the application. Therefore, it is required to produce an N-vinylcarboxylic acid amide (co) polymer having a desired molecular weight.
- the aqueous solution dropping polymerization method it is good to produce a polymer having a relatively low molecular weight.
- the viscosity of the solution becomes too high to be stirred, so the concentration needs to be lowered.
- the aqueous solution adiabatic polymerization method, photopolymerization method, reverse phase suspension polymerization method and the like are suitable for the production of high molecular weight N-vinylcarboxylic acid amide (co) polymers and have high production efficiency.
- Patent Document 1 an aqueous solution polymerization method in which a monomer containing N-vinylcarboxylic acid amide is polymerized in the presence of an inorganic salt having a saturation dissolution concentration or less is known (Patent Document 1).
- the amount of solid content in the gel can be increased by adding an inorganic salt, and there is no inconvenience in handling properties such as adhesion to a crusher, and it can be obtained as a water-containing gel having a hardness that can be pulverized by drying. it can.
- Patent Document 1 when a low molecular weight N-vinylcarboxylic acid amide (co) polymer is produced by the method of Patent Document 1, a large amount of salt is mixed in the polymer, so that there are limitations depending on the application. Furthermore, the gel cannot be adjusted to the desired physical properties unless the addition amount of the inorganic salt is increased. An excessively added inorganic salt causes metal corrosion and is industrially disadvantageous.
- Patent Document 3 a method for forming a crosslinked gel by copolymerizing with a crosslinking agent such as 1,2-ethanediol diglycidyl ether without using an inorganic salt
- the N-vinylcarboxylic acid amide (co) polymer obtained by the method of Patent Document 2 or Patent Document 3 is hydrolyzed in the presence of an acid or a base, the resulting vinylamine (co) polymer is an inorganic salt or It remains cross-linked with a cross-linking agent such as 1,2-ethanediol diglycidyl ether.
- a cross-linking agent such as 1,2-ethanediol diglycidyl ether.
- the vinylamine (co) polymer swells in water, it is difficult to make it into an aqueous solution, and it cannot be used as a flocculant or a papermaking chemical that requires high solubility.
- the present invention has been made in view of the above circumstances, and as a result of intensive studies by the inventor in view of the above problems, a gel-like N-vinylcarboxylic acid amide (co) having excellent handling properties even at a low molecular weight.
- the present inventors have found that a vinylamine (co) polymer excellent in solubility in water can be produced, and a polymer can be produced.
- the present invention has the following aspects.
- a water-insoluble N-vinylcarboxylic amide (co) polymer having a cross-linking bond which is obtained by hydrolyzing the N-vinylcarboxylic amide (co) polymer.
- N-vinylcarboxylic amide (co) polymer, wherein is water-soluble is water-soluble.
- the reduced viscosity at 25 ° C. of a 1 mol / L sodium chloride aqueous solution containing 0.1 g / dL of vinylamine (co) polymer obtained by hydrolyzing the N-vinylcarboxylic acid amide (co) polymer is 0.
- N-vinylcarboxylic amide (co) amide according to any one of [1] to [4], wherein the N-vinylcarboxylic amide (co) polymer is an N-vinylformamide (co) polymer. Co) polymer.
- N-vinylcarboxylic amide (co) polymer is an N-vinylformamide (co) polymer.
- N-vinylcarboxylic amide (co) polymer is an N-vinylcarboxylic amide (co) polymer obtained by adiabatic polymerization or photopolymerization.
- the N-vinylcarboxylic acid amide (co) polymer is an N-vinylcarboxylic acid amide (co) polymer obtained by adiabatic polymerization using ferrous sulfate as a polymerization initiator. [10] The production method according to any one of [10].
- the N-vinylcarboxylic acid amide (co) polymer is dried at 105 ° C. or lower and pulverized to obtain a powder.
- the manufacturing method as described.
- the content of the unsaturated aldehyde in the N-vinylcarboxylic acid amide (co) polymer is 0.05% by mass or less with respect to 100% by mass of the N-vinylcarboxylic acid amide (co) polymer.
- water-soluble means that the polymer is not water-soluble when measured by the following (measurement of insoluble content of N-vinylcarboxylic acid amide (co) polymer or vinylamine (co) polymer). It means that the amount of dissolved component is low and can be made into an aqueous solution. Specifically, as the amount of insoluble matter in the case of water solubility, when 495 g of water is added to 5 g of vinylamine (co) polymer pure content so as to be a 1% by mass vinylamine (co) polymer aqueous solution, Usually, 0 to 50 g of insoluble matter is preferably generated, 0 to 10 g is more preferable, and 0 to 1 g is more preferable.
- the “insoluble part” means an insoluble gel part in which the polymer has swollen by absorbing water.
- water-insoluble refers to the insoluble content as measured in the following examples (measurement of insoluble content of N-vinylcarboxylic acid amide (co) polymer or vinylamine (co) polymer). The amount is so large that it cannot be made into an aqueous solution. Specifically, the amount of insoluble matter in the case of water insolubility is 1% by weight of N-vinylcarboxylic acid amide (co) polymer or vinylamine (co) polymer aqueous solution so as to become an aqueous solution.
- the insoluble matter can be measured by the following method. (Measurement of insoluble content of N-vinylcarboxylic acid amide (co) polymer or vinylamine (co) polymer) 495 g of water was added to 5 g of pure N-vinylcarboxylic acid amide (co) polymer or vinylamine (co) polymer to make the total amount of the aqueous solution 500 g, and the mixture was stirred at 280 rpm for 1 hour. The residue on the wire mesh is washed with tap water, the residue on the wire mesh is regarded as an insoluble gel content, and the weight is measured.
- N-vinylcarboxylic acid amide (co) polymers having various molecular weights from high molecular weight to low molecular weight as gel polymers having excellent handleability. It is possible to obtain a high-quality vinylamine (co) polymer having excellent solubility by cutting at least a part of the cross-linking bond during hydrolysis of the polymer.
- a wide range of molecular weight vinylamine (co) polymers produced by the method of the present invention is extremely useful in various fields such as water treatment, especially flocculants in wastewater treatment, papermaking chemicals in the paper industry, paint additives, etc. It is a polymer that can be used in a wider range of fields.
- N-vinylcarboxylic acid amide (co) polymer in the first aspect of the present invention is a water-insoluble N-vinylcarboxylic acid amide (co) polymer having a cross-linking bond, which is obtained by hydrolyzing the polymer.
- the vinylamine (co) polymer obtained is water-soluble.
- the method for producing a vinylamine (co) polymer according to the second aspect of the present invention is a method for hydrolyzing an N-vinylcarboxylic acid amide (co) polymer having a cross-linking bond, wherein At least a portion of the crosslink is broken.
- Crosslinking refers to a structure derived from a crosslinking agent in an N-vinylcarboxylic amide (co) polymer obtained by copolymerizing an N-vinylcarboxylic amide and a crosslinking agent having an ethylenically unsaturated bond. Means a unit connection.
- N-vinylcarboxylic acid amide is a monomer 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 is preferable because of easy induction to a vinylamine (co) polymer. That is, the N-vinylcarboxylic amide (co) polymer is preferably an N-vinylformamide (co) polymer containing N-vinylformamide units.
- 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 ester, (meth) acrylonitrile, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl ( Dialkylaminoalkyl such as meth) acrylamide, dialkylaminoethyl (meth) acrylamide and salts thereof or quaternized or quaternized compounds, dialkylaminopropyl (meth) acrylamide and salts thereof or quaternized or quaternized salts (Meth) acrylates and salts thereof or quaternized or quaternized salts, diacetone acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate and the like are
- the “quaternized product” means a quaternary amine converted from an amine contained in the structure.
- the salt of (meth) acrylic acid is preferably a sodium salt or an ammonium salt.
- the salt of dialkylaminoalkyl (meth) acrylate is preferably a sodium salt or an ammonium salt, and the salt of a quaternized product is preferably a sodium salt or an ammonium salt.
- the content ratio of the N-vinylcarboxylic acid amide monomer in all monomers used in the polymerization reaction is usually 5 mol% or more, preferably 10 mol% or more, more preferably 50 mol% or more, and particularly preferably 85 mol%. ⁇ 100 mol%.
- the crosslinking agent is not included in all monomers.
- the content ratio of the N-vinylcarboxylic amide unit is usually 5 mol% or more, preferably 10 mol% or more, more preferably 50 mol with respect to all the structural units constituting the N-vinyl carboxylic acid amide (co) polymer. % Or more, particularly preferably 85 to 100 mol%.
- the crosslinking agent unit is not considered here.
- “structural unit” and “unit” mean a monomer unit constituting a polymer.
- the N-vinylcarboxylic acid amide (co) polymer excellent in handleability is a water-insoluble N-vinylcarboxylic acid amide (co) polymer having a cross-linking bond, and the polymer is hydrolyzed.
- the vinylamine (co) polymer obtained by decomposition must be water-soluble.
- the N-vinylcarboxylic acid amide (co) polymer is a co-polymer of N-vinylcarboxylic acid amide and a crosslinking agent that forms a crosslinking bond that is cleavable by at least a part of the crosslinking bond formed by hydrolysis. It can be obtained by polymerization.
- crosslinking agents include compounds having a plurality of acrylamide structures such as N, N′-methylenebisacrylamide and N, N′-propylenebisacrylamide; divinyl oxalate, divinyl malonate, divinyl succinate, Compounds having two or more vinyl ester structures in one molecule such as divinyl glutarate, divinyl adipate, divinyl pimelate, divinyl maleate, divinyl fumarate, trivinyl citrate, trivinyl trimellitic acid, tetravinyl pyromellitic acid; Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Such as polyfunctional (meth) acrylates such as Risuri Torr tri (meth) acrylate.
- polyfunctional (meth) acrylate which is easily hydrolyzed in the presence of an acid or a base.
- (meth) acrylate refers to acrylate and / or methacrylate.
- Polyfunctional (meth) acrylate means an ester of an alcohol having two or more hydroxyl groups and (meth) acrylic acid.
- an amide bond or an ester bond included in the cross-linked bond is converted into a carboxyl group or a hydroxyl group. This further improves the water solubility of the vinylamine (co) polymer obtained.
- One or more crosslinking agents can be used.
- the addition amount of the crosslinking agent is usually preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more with respect to 100% by mass of the raw material monomer of N-vinylcarboxylic amide. Moreover, 15 mass% or less is preferable normally, and 10 mass% or less is more preferable. Specifically, it is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and further preferably 2 to 10% by mass. If the addition amount is too small, a sufficient cross-linked structure cannot be formed, the gel strength is weak, and the handleability is not improved.
- the “raw material monomer” means all monomers including a crosslinking agent for synthesizing an N-vinylcarboxylic acid amide (co) polymer.
- the content ratio of the crosslinking agent unit is preferably 0.1 to 5 mol%, and preferably 0.5 to 3 mol% with respect to all the structural units constituting the N-vinylcarboxylic acid amide polymer. More preferred.
- the polymerization method of N-vinylcarboxylic acid amide is not particularly limited.
- an aqueous solution polymerization method as disclosed in JP-A-61-118406, a redox initiator and an azo compound as disclosed in WO00 / 58378 pamphlet are used. Adiabatic polymerization using a combination of initiators. Further, a photopolymerization method as disclosed in Japanese Patent No.
- a photopolymerization method in which an aqueous monomer solution is developed into a thin layer and irradiated with light while removing heat from one side and / or both sides of the thin layer;
- a nonionic surfactant emulsifier
- the adiabatic polymerization method and the photopolymerization method are preferable because of easy operation.
- a gel improver for relaxing adhesion of the hydrogel after polymerization to the apparatus may be coexisted.
- the “hydrated gel” is a gel-like substance containing water.
- Gel quality improving agents include polyalkylene glycols such as polyethylene glycol and polypropylene glycol; nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene carboxylic acid ester, and alkylene glycol alkyl ether Cationic surfactants such as tetraalkyl quaternary ammonium salts, trialkylbenzyl quaternary ammonium salts, and alkylpyridinium salts; silicones such as silicone oils and silicone emulsions.
- These gel improvers may be used in combination of two or more.
- the amount of the gel improver used is usually preferably 10 parts by mass or less and more preferably 1 part by mass or less with respect to 100 parts by mass of the monomer.
- a stabilizer such as a buffer solution may be used during the polymerization.
- the stabilizer include ammonium chloride and sodium phosphate.
- the amount of the stabilizer used is usually preferably 0.1 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the monomer. Moreover, 20 mass parts or less are preferable normally, and 15 mass parts or less are more preferable. Specifically, 0.1 to 20 parts by mass is preferable, and 1 to 15 parts by mass is more preferable.
- Polymerization is usually carried out at pH 5-9. When the pH is outside this range, loss due to hydrolysis of N-vinylcarboxylic acid amide increases.
- the pH is preferably adjusted with phosphoric acid.
- the polymerization initiation temperature is usually 0 to 40 ° C, preferably 0 to 30 ° C, more preferably 0 to 20 ° C.
- the molecular weight may be adjusted by using a chain transfer agent during the polymerization.
- 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 (sodium phosphinate).
- adiabatic polymerization it is preferably performed in an aqueous solution.
- the monomer is put into a heat insulating tank equipped with a vent pipe for blowing an inert gas such as nitrogen, and the monomer is vented by adding a radical polymerization initiator or after the ventilation.
- Polymerization is started by adding and mixing a radical polymerization initiator.
- concentration of the monomer in monomer aqueous solution is 20 mass% or more normally with respect to the total mass of aqueous solution, and 25 mass% or more is more preferable.
- 40 mass% or less is preferable normally, and 35 mass% or less is more preferable.
- the resulting gel will be soft and may cause the coalescence of gels with a reduced particle size, which may adversely affect the drying process and may deteriorate handling properties such as transportation and movement. . If the monomer concentration is too high, the amount of heat generated by the reaction becomes large, resulting in boiling polymerization, and aqueous solution adiabatic polymerization cannot be realized.
- the polymerization initiator is an azo initiator, a redox initiator, a peroxide initiator, or a combination thereof.
- water-soluble azo initiators include 2,2′-azobis (amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] Examples thereof include dihydrochloride and 4,4′-azobis (4-cyanovaleric acid).
- oil-soluble azo initiators include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile). 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-methoxy-2,4dimethyl) valeronitrile and the like.
- the redox polymerization initiator include a combination of t-butyl hydroperoxide, ammonium peroxodisulfate and sodium sulfite, sodium bisulfite, trimethylamine, tetramethylethylenediamine, ferrous sulfate and the like.
- ferrous sulfate is hardly affected by impurities in N-vinylcarboxylic acid amide, so that a sufficient polymerization rate can be maintained even if the purity of N-vinylcarboxylic acid amide is low.
- peroxide polymerization initiator examples include t-butyl hydroperoxide, ammonium peroxodisulfate or potassium, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t- Examples include butyl peroxy 2-ethylhexanoate.
- a combined system of a redox polymerization initiator and a water-soluble azo polymerization initiator is preferable.
- the redox polymerization initiator is t-butyl hydroperoxide combined with sodium sulfite, sodium hydrogen sulfite and ferrous sulfate, and 2,2′-azobis (2-amidinopropane) is used as the water-soluble azo polymerization initiator. It is preferable to use dihydrochloride in combination.
- the amount of the azo polymerization initiator and redox polymerization initiator used is usually preferably 0.001% by mass or more, more preferably 0.002% by mass or more, based on the monomer. 0.005 mass% or more is more preferable.
- 1 mass% or less is preferable normally, 0.5 mass% or less is more preferable, and 0.2 mass% or less is further more preferable. Specifically, it is preferably 0.001 to 1% by mass, more preferably 0.002 to 0.5% by mass, and further preferably 0.005 to 0.2% by mass.
- the amount is usually preferably 0.001% by mass or more, and more preferably 0.002% by mass or more based on the monomer.
- 0.1 mass% or less is preferable normally, and 0.07 mass% or less is more preferable. More specifically, the content is preferably 0.001 to 0.1% by mass, and more preferably 0.002 to 0.07% by mass.
- the aldehyde group-containing substance derived from the unreacted N-vinylcarboxylic acid amide during the hydrolysis step is a vinylamine (co-polymer) generated after hydrolysis.
- the polymerization conversion of N-vinylcarboxylic acid amide is higher. That is, the conversion rate is preferably 90% or more, more preferably 95% or more, further preferably 98% or more, and particularly preferably 99% or more.
- the monomer is developed into a thin layer and is irradiated with light while removing heat from one side and / or both sides of the thin layer.
- a light source having a dominant wavelength in the range of 250 to 500 nm is preferable.
- a high pressure mercury lamp, a fluorescent chemical lamp, a blue fluorescent lamp, or the like is used.
- the irradiation intensity can be arbitrarily changed depending on the amount of photoinitiator, the polymerization temperature, etc., but the range of 0.1 to 100 W / m 2 is preferable on the irradiated surface.
- the concentration of the monomer in the aqueous monomer solution is usually preferably 20% by mass or more and more preferably 25% by mass or more with respect to the total mass of the aqueous monomer solution.
- 90 mass% or less is preferable normally, and 80 mass% or less is more preferable. Specifically, 20 to 90% by mass is preferable, and 25 to 80% by mass is more preferable.
- the thickness of the thin layer during polymerization is usually preferably 1 mm or more, more preferably 2 mm or more, and further preferably 5 mm or more. Moreover, usually 50 mm or less is preferable, 30 mm or less is more preferable, and 20 mm or less is further more preferable.
- the thin layer is too thin, the polymer cannot be produced efficiently, and when the thin layer is too thick, the heat generated during the polymerization cannot be sufficiently removed. It is preferable to remove oxygen from the monomer aqueous solution prior to polymerization. Oxygen removal is industrially performed by ventilating an inert gas such as nitrogen or helium. Also, the aqueous monomer solution is adjusted to an appropriate starting temperature prior to polymerization. The starting temperature is usually preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, and further preferably 0 ° C. or higher.
- 70 degrees C or less is preferable normally, 50 degrees C or less is more preferable, and 30 degrees C or less is further more preferable. More specifically, it is preferably ⁇ 20 to 70 ° C., more preferably ⁇ 10 to 50 ° C., and further preferably 0 to 30 ° C.
- the radical photopolymerization initiator used in the photopolymerization method may be allowed to coexist in the monomer aqueous solution at the time of polymerization. As a photoinitiator, it can select from a well-known compound suitably.
- Examples include benzophenone series, benzoin series, benzoin alkyl ether series, benzyl dimethyl ketal series, ⁇ -hydroxy ketone series, bisacylphosphine oxide series photopolymerization initiators, and the like.
- the amount of the photopolymerization initiator used is usually preferably 0.001% by mass or more, more preferably 0.002% by mass or more, and further preferably 0.005% by mass or more based on the monomer. Moreover, 1 mass% or less is preferable normally, 0.5 mass% or less is more preferable, and 0.2 mass% or less is further more preferable. More specifically, the content is preferably 0.001 to 1% by mass, more preferably 0.002 to 0.5% by mass, and further preferably 0.005 to 0.2% by mass.
- One or two or more photopolymerization initiators can be used. The photoinitiator can be used in combination with an appropriate sensitizer.
- the sensitizer examples include amines, halides such as iodonium salts, and thioxanthones. Specific examples include methyldiethanolamine, bisdiethylaminobenzophenone, diethylthioxanthone, isopropylthioxanthone and the like. In some cases, an azo polymerization initiator may be used in combination as a polymerization initiator.
- 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyrate Nitrile
- 2,2′-azobis (2-amidinopropane) dihydrochloride 2,2′-azobis [2- (2-imidazolin-2-yl) propane] or its dihydrochloride or diacetate thereof
- 2,2′-azobisisobutyric acid dimethyl ester 4,4′-azobis (4-cyanovaleric acid) or two of them
- Examples thereof include sodium salt or dipotassium salt thereof.
- the amount of the azo compound used is usually preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.2% by mass or less with respect to 100% by mass of the monomer.
- 0.001 mass% or more is preferable normally, 0.002 mass% or more is more preferable, and 0.005 mass% or more is further more preferable.
- it is preferably 0.001 to 1% by mass, more preferably 0.002 to 0.5% by mass, and still more preferably 0.005 to 0.2% by mass.
- the N-vinylcarboxylic acid amide polymer can be obtained as a massive hydrous gel.
- the water content of the water-containing gel is preferably 10 to 80%.
- the “water content” means the amount of water in the water-containing gel with respect to the total mass of the obtained water-containing gel.
- the moisture content can be determined by a method in which a precisely weighed hydrated gel is heated at 110 ° C. for 120 minutes and the reduced amount obtained by the gravimetric method is used as the moisture content.
- the obtained massive hydrous gel is usually pulverized and pulverized into particles.
- the longest diameter of the granular material obtained by pulverization is usually preferably 5 cm or less, preferably 2 cm or less, and more preferably 1 cm or less. Further, the shortest diameter of the granular material is usually preferably 1 mm or more, more preferably 3 mm or more, and further preferably 5 mm or more. More specifically, it is preferably 1 mm to 5 cm, more preferably 3 mm to 2 cm, and even more preferably 5 mm to 1 cm.
- the crushing method include a method of cutting the gel with a cutter or the like, a method of cutting the gel by extrusion with a meat chopper or the like, and the like.
- the hole diameter of the die of the meat chopper corresponds to the longest diameter, and is usually preferably 5 cm or less, more preferably 2 cm or less, and further preferably 1 cm or less. Moreover, 1 mm or more is usually preferable, 3 mm or more is more preferable, and 5 mm or more is further more preferable. More specifically, it is preferably 1 mm to 5 cm, more preferably 3 mm to 2 cm, and even more preferably 5 mm to 1 cm.
- An auxiliary agent may be used to suppress adhesion between particles. Usually, surfactants and the like are used in addition to various oils such as polyalkylene glycols and silicone oils.
- the water-containing gel particles obtained above can be dried until the water content becomes 5 to 30% by mass.
- the moisture content here means the amount of water in the hydrogel granules relative to the total mass of the hydrogel granules.
- various known devices such as a band dryer, a vibration fluidized dryer, a disk dryer, a conical dryer and the like are used.
- the drying conditions can be selected as appropriate. However, if the temperature is too low, the drying efficiency is poor, and if the temperature is too high, the polymer deteriorates. It has also been found that by increasing the drying temperature, aldehydes that cause insolubilization when hydrolyzed increase. In particular, an increase in ⁇ , ⁇ -unsaturated aldehyde (hereinafter also referred to as “unsaturated aldehyde”) is remarkable.
- ⁇ , ⁇ -unsaturated aldehyde means a compound containing an unsaturated bond and an aldehyde group in the molecule. Specifically, crotonaldehyde, 2,4-hexadienal (sorbine aldehyde), cinnamon And aldehydes. Therefore, the drying temperature is usually preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher. Moreover, normally 105 degrees C or less is preferable, 100 degrees C or less is more preferable, and 100 degrees C or less is further more preferable. More specifically, it is preferably 40 to 105 ° C, more preferably 50 to 100 ° C, and further preferably 60 to 100 ° C.
- the dried polymer can be pulverized by a known method.
- the powdering method include a method using a Willet pulverizer, a ball mill pulverizer, a hammer mill pulverizer, or the like.
- the particle size of the powder can be arbitrarily determined. However, if it is too large, it takes time to dissolve, and if it is too small, it is not preferable because it causes the occurrence of so-called mako and deterioration of the working environment due to fine powder.
- the size of the powder is preferably such that it passes through 4 mesh with a sieve mesh, and more preferably passes through 10 mesh. Further, the size remaining in 500 mesh is preferable, and the size remaining in 100 mesh is more preferable.
- the powder having a size that passes through 4 meshes and remains in 500 meshes preferably accounts for 80% or more of the total weight of the powder, and more preferably 90% or more. More specifically, the average particle diameter of the powder after drying is preferably 0.25 to 5 mm, more preferably 0.25 to 2 mm.
- the average particle diameter can be measured by the following method. (Measurement of average particle size) Opening (unit: ⁇ m) 1700, 1000, 710, 500, 250, 75 each standard sieve and the weight of the saucer are measured, they are overlapped, and 10 g of powdery polymer is put on the top sieve did.
- the content of ⁇ , ⁇ -unsaturated aldehyde in the obtained powdered N-vinylcarboxylic acid amide (co) polymer is preferably 0.05% by mass or less based on the polymer. More preferably, it is 0.03 mass% or less. When the amount is more than 0.05% by mass, the amount of the insolubilization inhibitor to be described later increases, resulting in poor economic efficiency.
- the method for producing a vinylamine (co) polymer according to the second aspect of the present invention is a method for producing a vinylamine (co) polymer by hydrolyzing an N-vinylcarboxylic acid amide (co) polymer having a crosslink.
- the N-vinylcarboxylic acid amide (co) polymer having a crosslink in the first embodiment of the present invention is a vinylamine (co) polymer that is suitable for use in papermaking chemicals and flocculants by hydrolyzing a part or all of it. It becomes.
- the N-vinylcarboxylic acid amide polymer having a crosslink is converted into a vinylamine (co) polymer by contact with an acid or a base, and at least a part of the crosslink is cleaved.
- “At least a part of the cross-linked bond is cleaved” means that an amide bond or an ester bond included in the cross-linked bond is hydrolyzed.
- all amide bonds or ester bonds in the crosslinked structure may not be hydrolyzed, and some amide bonds or ester bonds may be hydrolyzed.
- the amide bond or ester bond of the cross-linked bond to be hydrolyzed is preferably 80 to 100 mol%, and preferably 90 to 100 mol% with respect to the total number of moles of the amide bond or ester bond included in the cross-linked bond. Is more preferable.
- the N-vinylcarboxylic acid amide unit to be hydrolyzed is preferably 10 to 100 mol%, more preferably 10 to 90 mol%, based on all N-vinylcarboxylic acid amide units.
- a hydrolysis method a method of drying an N-vinylcarboxylic acid amide polymer having a cross-linked bond and suspending it in water in the presence of an acid or a base to hydrolyze, a cross-link bond is used.
- a method of crushing a bulk gel of N-vinylcarboxylic acid amide polymer having a granular product, mixing the granular material with an acid or a base and hydrolyzing it, and a N-vinylcarboxylic acid amide polymer having a cross-linking bond examples include a method of dispersing in a hydrocarbon-based dispersion medium in a water-in-oil type and hydrolyzing by adding an acid or base, but in order to perform uniform hydrolysis, in the presence of an acid or base, It is preferable to suspend the reaction. In order to improve productivity and transportability, it is desirable to carry out the reaction under conditions where the polymer concentration (concentration of N-vinylcarboxylic acid amide polymer) is as high as possible.
- the polymer concentration is determined by the balance between the ability of the dissolution apparatus and the economy. Usually, when suspended in water in the presence of an acid or base, it is preferably 0.1% by weight or more based on the total mass of the suspension. 1% by weight or more is more preferable, and 2% by weight or more is more preferable. Moreover, usually 30 weight% or less is preferable, 20 weight% or less is more preferable, and 15 weight% or less is further more preferable. More specifically, it is preferably 0.1 to 30% by weight or less, more preferably 1 to 20% by weight, and further preferably 2 to 15% by weight. In the case of a dispersion dispersed in a water-in-oil type, the polymer concentration is preferably 0.1 to 50% by weight, more preferably 5 to 40% by weight, based on the total mass of the dispersion.
- the aldehyde group-containing substance derived from the unreacted N-vinylcarboxylic acid amide during the hydrolysis step is a vinylamine (co-polymer) generated after hydrolysis. )
- a cross-linked structure is formed and it becomes easy to insolubilize in water. Therefore, you may perform an insolubilization prevention process using an insolubilization prevention agent before a hydrolysis.
- the insolubilization inhibitor is a substance to which a substance having high reactivity with an aldehyde group that causes an oxime reaction or an oxidation-reduction reaction with an aldehyde group prior to hydrolysis or in parallel with the hydrolysis is added.
- substances include hydroxylamine or its hydrochloride or sulfate, hydrogen peroxide, sodium borohydride, ascorbic acid as disclosed in JP-A-5-86127 and JP-A-5-125109.
- hydroxylamine particularly preferred are hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate, sodium borohydride, ammonia, ammonium chloride, ammonium sulfate and the like.
- the amount of the insolubilization inhibitor used varies depending on the amount of monomer remaining in the N-vinylcarboxylic acid amide polymer or the amount of aldehydes present as impurities, but is usually 0.1% relative to 100 parts by mass of the polymer. More than mass part is preferable and 0.2 mass part or more is more preferable. Moreover, 10 mass parts or less are preferable normally, and 4 mass parts or less are more preferable.
- the amount is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 4 parts by weight with respect to 100 parts by weight of the polymer.
- the insolubilization inhibitor may be added after the polymer powder is dissolved, or may be added in advance to water in which the polymer powder is dissolved. Further, it may be added to the hydrogel or polymer powder.
- the N-vinylcarboxylic acid amide (co) polymer solution having a crosslink obtained as described above can promote hydrolysis by heating.
- the hydrolysis temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher.
- 180 degrees C or less is preferable, 140 degrees C or less is more preferable, and 100 degrees C or less is further more preferable. More specifically, 30 to 180 ° C. is preferable, 50 to 140 ° C. is more preferable, and 60 to 100 ° C. is still more preferable. If the hydrolysis is performed at a temperature that is too low, it takes time to cut at least a part of the cross-linking bond, and a uniform aqueous solution is not obtained. On the other hand, if hydrolysis is carried out at a temperature that is too high, there is a risk of promoting the deterioration of the polymer.
- the heating time may be determined according to the desired hydrolysis rate, but it may be less than 48 hours, preferably less than 24 hours, more preferably less than 12 hours, because deterioration may be accelerated when heated at a high temperature for a long time. is there.
- the acid or base used for the hydrolysis may remain in the vinylamine (co) polymer. These remaining acids or bases may be neutralized as necessary.
- Hydrolysis is preferably performed with a strong acid or a strong base.
- Suitable acids for the hydrolysis are, for example, hydrogen halides (hydrochloric acid in aqueous solution), sulfuric acid, nitric acid, phosphoric acid, (ortho-, meta-polyphosphoric acid) among inorganic acids.
- organic acids for example, carboxylic acids having 1 to 5 carbon atoms such as formic acid, acetic acid and propionic acid, or aliphatic or aromatic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid. Of these, hydrochloric acid is preferred.
- Suitable bases for hydrolysis are the hydroxides of the metals of groups 1 and 2 of the periodic table. Specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and the like. Also suitable are ammonia and alkyl derivatives of ammonia, such as alkyl- or arylamines. Examples of such amines include triethylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, and aniline. Among these, ammonia, sodium hydroxide solution, and potassium hydroxide solution are preferable.
- the amount of acid or base used varies depending on the desired hydrolysis rate, but is the total amount of the N-vinylcarboxylic acid amide copolymerized with the cross-linking agent used in the production of the target vinylamine (co) polymer.
- the molar equivalent is usually 0.8 times or more, more preferably 1 time molar equivalent or more.
- 2 times molar equivalent or less is preferable normally, and 1.5 times molar equivalent or less is more preferable.
- 0.8 to 2 times molar equivalent is preferable, and 1 to 1.5 times molar equivalent is more preferable.
- the acid or base is preferably dissolved in advance and subjected to a hydrolysis reaction as a solution.
- the rate of hydrolysis is usually preferably 0.1 mol% or more, more preferably 1 mol% or more, as a ratio to the N-vinylcarboxylic acid amide monomer unit.
- 100 mol% or less is preferable normally and 95 mol% or less is more preferable. More specifically, it is preferably 0.1 to 100 mol%, more preferably 1 to 95 mol%.
- the vinylamine (co) polymer in the third embodiment of the present invention is obtained by hydrolyzing an N-vinylcarboxylic acid amide (co) polymer.
- the vinylamine (co) polymer is a (co) polymer containing vinylamine units and is water-soluble.
- it is a crosslinking agent unit, Comprising: The crosslinking agent unit by which one part structure (amide bond or ester bond) in the crosslinking agent unit was hydrolyzed and converted into the carboxyl group or the hydroxyl group is included.
- the vinylamine unit is preferably 9.5 to 99.9 mol%, more preferably 10 to 90 mol%, based on all the structural units constituting the vinylamine (co) polymer.
- the hydrolyzed crosslinking agent unit is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, based on the total crosslinking agent units.
- the vinylamine (co) polymer preferably has a reduced viscosity at 25 ° C. of a 1 mol / L sodium chloride aqueous solution containing 0.1 g / dL of the polymer of 0.1 to 10 dL / g.
- the reduced viscosity can be measured by the following method. (Measurement of reduced viscosity) A vinylamine (co) polymer aqueous solution is dissolved in 1 N saline to a concentration of 0.1 g / dL of pure water to obtain a sample solution, and the flow time is measured at 25 ° C. using an Ostwald viscometer.
- the ratio (molar ratio) between the hydrolyzed crosslinking agent unit and the vinylamine unit is preferably 95: 5 to 99.9: 0.1, and 97: 3 to 99.5: 0.5 is more preferable. By setting it as this numerical range, the water solubility of the obtained vinylamine (co) polymer increases more.
- the N-vinylcarboxylic acid amide (co) polymer having a cross-linked bond obtained according to the present invention has a high gel strength and excellent handleability, so that it is possible to produce a polymer having a wide molecular weight.
- the cross-linked bond formed by copolymerization with a cross-linking agent is easily hydrolyzed with a strong acid or strong base, the hydrolyzed vinylamine (co) polymer is excellent in solubility, particularly in the field of water treatment. It is useful as a flocculant in wastewater treatment and a papermaking agent in the paper industry.
- the N-vinylcarboxylic acid amide (co) polymer is preferably obtained by polymerizing N-vinylformamide and polyethylene glycol # 600 diacrylate, polyethylene glycol # 600 dimethacrylate or divinyl adipate as a crosslinking agent. .
- the hydrolysis of the N-vinylcarboxylic acid amide (co) polymer preferably uses a base, and sodium hydroxide is particularly preferable.
- Example 1 In 68 parts by weight of deionized water, 0.3 part by weight of polyethylene glycol (average molecular weight 20000), 0.5% by weight of sodium phosphinate (based on monomer) as a chain transfer agent are dissolved, and then N-vinylformamide (purity) 99 parts by mass) 32 parts by weight were mixed. In the resulting aqueous monomer solution, 7% by mass of polyethylene glycol # 600 diacrylate (trade name: NK Ester A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.) is dissolved with respect to the raw material monomer, and then dissolved in phosphoric acid. The monomer aqueous solution was adjusted to pH 6.3 to obtain a monomer adjusting solution.
- the monomer adjustment solution was cooled to ⁇ 2 ° C., then transferred to an adiabatic reaction vessel equipped with a thermometer and subjected to nitrogen aeration for 15 minutes, and then 2,2′-azobis (2-amidinopropane) dihydrochloride ( Product Name: Wako Pure Chemicals V-50 0.15% by mass (based on monomer) and t-butyl hydroperoxide (product name: Perfume H-69, manufactured by Nippon Oil & Fats) 0.1% by mass (based on single amount) Body) was added as a 10% by mass aqueous solution, and then 0.1% by mass sodium bisulfite (based on the monomer) was added as a 10% by mass aqueous solution to initiate adiabatic polymerization.
- 2,2′-azobis (2-amidinopropane) dihydrochloride Product Name: Wako Pure Chemicals V-50 0.15% by mass (based on monomer) and t-butyl hydroperoxide (product name: Perf
- the system temperature reached 92 ° C., and then kept in the reaction vessel for another 60 minutes. Thereafter, the produced polymer was taken out from the reaction vessel and crushed with a meat chopper. The obtained gel granules maintained a fine-grained shape and had good handleability. Next, the gel granule was dried for 1.5 hours with a ventilator so that the temperature of the polymer was 105 ° C., and then pulverized to obtain a powder.
- the ⁇ , ⁇ -unsaturated aldehyde content in this powder N-vinylformamide (co) polymer was measured and found to be 0.0076% by mass with respect to 100% by mass of the N-vinylformamide (co) polymer.
- Example 2 An N-vinylformamide (co) polymer was prepared in the same manner as in Example 1 except that polyethylene glycol # 600 diacrylate was changed to polyethylene glycol # 600 dimethacrylate (trade name: NK Ester 14G manufactured by Shin-Nakamura Chemical Co., Ltd.). However, the obtained gel granular material maintained a fine-grained shape and had good handleability. Next, hydrolysis was performed in the same manner as in Example 1 to obtain a vinylamine (co) polymer aqueous solution (concentration: 10% by mass) in which 40 mol% of all N-vinylformamide units were converted to vinylamine units. . This aqueous solution was diluted and dissolved in 1% by mass, and the insoluble matter was measured. The reduced viscosity of the obtained vinylamine (co) polymer was 0.6 dL / g. The results are shown in Table 1.
- Example 3 An N-vinylformamide (co) polymer was obtained in the same manner as in Example 1 except that polyethylene glycol # 600 diacrylate was changed to divinyl adipate, and the gel particles obtained were fine particles. The shape was maintained and the handleability was good. Next, hydrolysis was performed in the same manner as in Example 1 to obtain a vinylamine (co) polymer aqueous solution (concentration: 10% by mass) in which 40 mol% of all N-vinylformamide units were converted to vinylamine units. . This aqueous solution was diluted and dissolved in 1% by mass, and the insoluble matter was measured. The reduced viscosity of the obtained vinylamine (co) polymer was 0.6 dL / g. The results are shown in Table 1.
- Example 4 50 parts by mass of N-vinylformamide (purity 99% by mass) was mixed with 50 parts by mass of deionized water, and 0.2% by mass of polyethylene glycol # 600 After the acrylate (trade name: NK Ester A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.) was dissolved, the monomer aqueous solution was adjusted to pH 6.3 with phosphoric acid to obtain a monomer adjusting solution.
- acrylate trade name: NK Ester A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.
- a chain transfer agent 0.5% by mass of an aqueous solution of 10% by weight of sodium phosphinate (based on the monomer) and a photopolymerization initiator D4265 (manufactured by Ciba Specialty Chemicals) as a chain transfer agent were added to the monomer preparation solution in an amount of 0.4% by weight
- nitrogen aeration was performed for 20 minutes while cooling to 10 ° C. to remove dissolved oxygen.
- a polyethylene terephthalate film [base film 12 ⁇ m thickness, PVDC (polyvinylidene chloride) coat 4 ⁇ m thickness] is laid on the bottom surface of a tray-like container (bottom surface 200 mm ⁇ 200 mm) made of stainless steel.
- the fluorescent chemical lamp was irradiated so as to have an intensity of 10 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 irradiation intensity was increased to 20 W / m 2 and the polymerization was continued for another 90 minutes. The highest polymerization temperature was observed 85 minutes after the start of irradiation.
- the produced polymer was taken out from the reaction vessel to obtain a polymer gel.
- the polymer gel was crushed into 2 cm square pieces, and the crushed gel pieces were treated with a meat chopper with a die hole diameter of 4.8 mm to obtain a granular material in which the gel pieces were reduced to 5 mm square or less. .
- the obtained gel granules maintained a fine-grained shape and had good handleability.
- the gel granule was dried for 1.5 hours with a ventilating dryer at 105 ° C. and then pulverized to obtain a powder.
- Example 2 hydrolysis was performed in the same manner as in Example 1 to obtain a vinylamine (co) polymer aqueous solution (concentration: 10% by mass) in which 40 mol% of all N-vinylformamide units were converted to vinylamine units. .
- This aqueous solution was diluted and dissolved in 1% by mass, and the insoluble matter was measured.
- the reduced viscosity of the obtained vinylamine (co) polymer was 0.5 dL / g. The results are shown in Table 1.
- Example 5 N-vinylformamide having a purity of 99% was changed to N-vinylformamide having a purity of 92%.
- 0.03% by mass of ferrous sulfate (based on simple substance) Polymerization was carried out in the same manner as in Example 1 except that the monomer was added as a 5% by mass aqueous solution.
- the system temperature reached 91 ° C. 150 minutes after the start of polymerization, and a sufficient polymerization rate could be maintained even with low-purity N-vinylformamide.
- the obtained N-vinylformamide (co) polymer gel granules maintained a fine-grained shape and had good handleability.
- Example 2 hydrolysis was performed in the same manner as in Example 1 to obtain a vinylamine (co) polymer aqueous solution (concentration: 10% by mass) in which 40 mol% of all N-vinylformamide units were converted to vinylamine units. .
- This aqueous solution was diluted and dissolved in 1% by mass, and the insoluble matter was measured.
- the reduced viscosity of the obtained vinylamine (co) polymer was 0.5 dL / g. The results are shown in Table 1.
- Example 1 An N-vinylformamide (co) polymer was obtained in the same manner as in Example 1 except that polyethylene glycol # 600 diacrylate was not added. It became difficult to handle. Next, hydrolysis was performed in the same manner as in Example 1 to obtain a vinylamine (co) polymer aqueous solution (concentration: 10% by mass) in which 40 mol% of all N-vinylformamide units were converted to vinylamine units. . This aqueous solution was diluted and dissolved in 1% by mass, and the insoluble matter was measured. The reduced viscosity of the obtained vinylamine (co) polymer was 0.6 dL / g. The results are shown in Table 1.
- Example 2 The same procedure as in Example 2 was performed except that polyethylene glycol # 600 diacrylate was not added, and an N-vinylformamide (co) polymer was obtained. It became difficult to handle.
- Example 2 hydrolysis was performed in the same manner as in Example 1 to obtain a vinylamine (co) polymer aqueous solution (concentration: 10% by mass) in which 40 mol% of all N-vinylformamide units were converted to vinylamine units. .
- This aqueous solution was diluted and dissolved in 1% by mass, and the insoluble matter was measured.
- the reduced viscosity of the obtained polymer was 0.6 dL / g. The results are shown in Table 1.
- Example 3 The same operation as in Example 1 was performed to obtain an N-vinylformamide (co) polymer.
- the obtained gel granular material maintained the shape of fine particles and had good handleability.
- the gel particles obtained in Examples 1 to 5 maintained a fine particle shape and had good handleability. Further, when this N-vinylformamide (co) polymer was hydrolyzed, a part of the cross-linked bond was cleaved, and a vinylamine (co) polymer excellent in solubility could be obtained. On the other hand, the gel particles obtained in Comparative Examples 1 and 2 were difficult to handle because most of the gel particles were coalesced to form a strand.
- the gel granular material obtained in Comparative Example 3 maintained a fine particle shape and good handleability, but was not hydrolyzed, so the partial structure of the cross-linked bond was not cut and an insoluble content was obtained. Was present in large quantities.
- the gel granular material obtained in Comparative Example 4 maintained a fine-grained shape and had good handleability.
- this N-vinylformamide (co) polymer was hydrolyzed, it showed cross-linking. None of the portions were cleaved, and the hydrolyzed vinylamine (co) polymer had a large amount of insoluble matter.
- the present invention can be widely applied as a method for producing a vinylamine (co) polymer.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本願は、2013年11月8日に、日本に出願された特願2013-231762号に基づき優先権を主張し、その内容をここに援用する。
N-ビニルカルボン酸アミド(共)重合体は、上記のようにその用途に応じ、高分子量の重合体から低分子量の重合体まで幅広い分子量の重合体が使用される。そのため、所望の分子量のN-ビニルカルボン酸アミド(共)重合体を製造することが求められる。しかしながら、ひとつの重合法で幅広い分子量の重合体を効率よく製造することは困難である。たとえば水溶液滴下重合法では比較的低分子量の重合体を製造する場合はよいが、高分子量の重合体を製造しようとすると溶液の粘度が上がりすぎ撹拌できなくなるため、濃度を下げる必要がある。一方水溶液静置断熱重合法や、光重合法、逆相懸濁重合法等は、高分子量のN-ビニルカルボン酸アミド(共)重合体の製造に適しており、製造効率も高い。しかし重合終了時に重合体水溶液あるいはその懸濁液を取り出す必要がある。そのため、比較的分子量の低い重合体を製造しようとすると重合終了後に得られるゲルが柔らかいため、解砕機に付着するなど取り扱い性が悪い。このため、幅広い分子量のN-ビニルカルボン酸アミド(共)重合体を製造するために、水溶液静置断熱重合法や、光重合法、逆相懸濁重合法等は不向きである。
この課題を解決する方法として、飽和溶解濃度以下の無機塩の存在下、N-ビニルカルボン酸アミドを含む単量体を重合する水溶液重合法が知られている(特許文献1)。無機塩が添加されることでゲル中の固形分量を増加させることができ、解砕機に付着するなどの取り扱い性における不都合がなく、乾燥により粉砕処理可能な硬さの含水ゲルとして取得することができる。
しかしながら、特許文献1の方法で低分子量のN-ビニルカルボン酸アミド(共)重合体を製造した場合、重合体に多量の塩が混入するため用途によっては制限を受ける。さらに無機塩の添加量を増やさないとゲルを所望の物性に調節できない。過剰に添加された無機塩は金属腐食の原因となるため、工業的に不利である。
一方、高強度のゲルを製造する方法として、無機塩を使用せず、1,2-エタンジオールジグリシジルエーテルといった架橋剤と共重合することで架橋ゲルとする方法も知られている(特許文献2、特許文献3)。
しかしながら、特許文献2あるいは特許文献3の方法で得たN-ビニルカルボン酸アミド(共)重合体を酸又は塩基の存在下で加水分解した場合、得られるビニルアミン(共)重合体は無機塩又は1,2-エタンジオールジグリシジルエーテルのような架橋剤で架橋したままである。この場合、ビニルアミン(共)重合体は水中で膨潤するため水溶液にすることは難しく、高溶解性が必要な凝集剤や製紙用薬剤として使用できない。
ここで「水不溶性」とは、以下実施例に記載した(N-ビニルカルボン酸アミド(共)重合体、又はビニルアミン(共)重合体の不溶解分測定)で測定した場合の不溶解分の量が多く、水溶液にすることができないことをいう。具体的には水不溶性の場合の不溶解分の量としては、1質量%のN-ビニルカルボン酸アミド(共)重合体、又はビニルアミン(共)重合体水溶液となるようにN-ビニルカルボン酸アミド(共)重合体、又はビニルアミン(共)重合体純分5gに水を495g加えたときに、通常50gよりも多い。また、粒子状の重合体を水に溶解させようとした場合に重合体が膨潤するのみで完全に溶解しない場合も水不溶性と定義する。
不溶解分は以下の方法で測定することができる。
(N-ビニルカルボン酸アミド(共)重合体、又はビニルアミン(共)重合体の不溶解分の測定)
N-ビニルカルボン酸アミド(共)重合体、又はビニルアミン(共)重合体純分5gに495gの水を加え水溶液全量を500gとし、280回転/分で1時間攪拌した後、水溶液を目開き180μmの金網を通して濾過し、金網上の残物を水道水で洗浄し、金網上の残物を不溶解ゲル分とみなし重量を測定する。
<N-ビニルカルボン酸アミド(共)重合体>
本発明の第一の態様におけるN-ビニルカルボン酸アミド(共)重合体は、架橋結合を有する水不溶性のN-ビニルカルボン酸アミド(共)重合体であって、前記重合体を加水分解して得られるビニルアミン(共)重合体が水溶性である。
また本発明第二の態様におけるビニルアミン(共)重合体の製造方法は、架橋結合を有するN-ビニルカルボン酸アミド(共)重合体を加水分解し製造する方法であって、前記加水分解により前記架橋結合の少なくとも一部が切断される。
「架橋結合」とは、N-ビニルカルボン酸アミドと、エチレン性不飽和結合を有する架橋剤が共重合することにより得られるN-ビニルカルボン酸アミド(共)重合体における、架橋剤由来の構成単位の結合のことを意味する。
N-ビニルカルボン酸アミド(共)重合体を構成する全構成単位に対し、N-ビニルカルボン酸アミド単位の含有割合は、通常5モル%以上、好ましくは10モル%以上、更に好ましくは50モル%以上、特に好ましくは85~100モル%である。ただしここで架橋剤単位は考慮しないものとする。ここで「構成単位」及び「単位」とは、重合体を構成するモノマー単位を意味する。
架橋結合の一部が加水分解により切断されると、架橋結合に含まれるアミド結合又はエステル結合がカルボキシル基又はヒドロキシル基に変換される。これにより得られるビニルアミン(共)重合体の水溶性がより向上する。
架橋剤は1種でも2種以上でも使用できる。
N-ビニルカルボン酸アミド重合体を構成する全構成単位に対して、架橋剤単位の含有割合は、0.1~5モル%であることが好ましく、0.5~3モル%であることがより好ましい。
上記の重合開始剤の中ではレドックス系重合開始剤と水溶性アゾ系重合開始剤の併用系が好ましい。そして、レドックス系重合開始剤としてはt-ブチルハイドロパーオキサイドと亜硫酸ナトリウムや亜硫酸水素ナトリウム、硫酸第一鉄を組合せ、水溶性アゾ系重合開始剤として2,2’-アゾビス(2-アミジノプロパン)二塩酸塩を併用することが好ましい。アゾ系重合開始剤とレドックス系重合開始剤の使用量は、アゾ系重合開始剤の場合、単量体に対し、通常0.001質量%以上が好ましく、0.002質量%以上がより好ましく、0.005質量%以上がさらに好ましい。また、通常1質量%以下が好ましく、0.5質量%以下がより好ましく、0.2質量%以下がさらに好ましい。具体的には0.001~1質量%が好ましく、0.002~0.5質量%がより好ましく、0.005~0.2質量%がさらに好ましい。レドックス系開始剤の場合、単量体に対し、通常0.001質量%以上が好ましく、0.002質量%以上がより好ましい。また、通常0.1質量%以下が好ましく、0.07質量%以下がより好ましい。より具体的には、0.001~0.1質量%であることが好ましく、0.002~0.07質量%であることがより好ましい。前記使用量とすることで、重合反応が安定して行われる。
重合開始剤は1種でも2種以上でも使用できる。
重合時の薄層の厚さは、通常1mm以上が好ましく、2mm以上がより好ましく、5mm以上がさらに好ましい。また、通常50mm以下が好ましく、30mm以下がより好ましく、20mm以下がさらに好ましい。具体的には1~50mmが好ましく、2~30mmがより好ましく、5~20mmがさらに好ましい。薄層の厚さが薄すぎる場合は効率的に重合体を製造できず、薄層が厚すぎる場合は重合時の発熱を充分に除熱できない。
単量体水溶液は重合に先立って酸素を除くことが好ましい。酸素の除去は、工業的には、窒素、ヘリウム等の不活性ガスを通気することにより行われる。また、単量体水溶液は重合に先立って適切な開始温度に調節される。開始温度は、通常-20℃以上が好ましく、-10℃以上がより好ましく、0℃以上がさらに好ましい。また、通常70℃以下が好ましく、50℃以下がより好ましく、30℃以下がさらに好ましい。より具体的には、-20~70℃が好ましく、-10~50℃がより好ましく、0~30℃がさらに好ましい。
光重合法で使用されるラジカル系光重合開始剤は、重合時に単量体水溶液中に共存させればよい。光重合開始剤としては、公知の化合物から適宜選定することが出来る。例えば、ベンゾフェノン系、ベンゾイン系、ベンゾインアルキルエーテル系、ベンジルジメチルケタール系、α-ヒドロキシケトン系、ビスアシルフォスフィンオキサイド系光重合開始剤などが挙げられる。具体的には、ベンゾフェノン、ベンゾイン、ベンゾインエチルエーテル、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-1-ブタン-1-オン、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-1-ペンチルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、(2,4,6-トリメチルベンゾイル)-ジフェニルフォスフィンオキサイド等が例示される。光重合開始剤の使用量は、単量体に対し、通常0.001質量%以上が好ましく、0.002質量%以上がより好ましく、0.005質量%以上がさらに好ましい。また、通常1質量%以下が好ましく、0.5質量%以下がより好ましく、0.2質量%以下がさらに好ましい。より具体的には、0.001~1質量%が好ましく、0.002~0.5質量%がより好ましく、0.005~0.2質量%がさらに好ましい。光重合開始剤は1種でも2種以上でも使用できる。
光開始剤は適当な増感剤と併用することが出来る。増感剤としては、例えば、アミン類、ヨードニウム塩等のハロゲン化物、チオキサントン類等が挙げられる。具体的には、メチルジエタノールアミン、ビスジエチルアミノベンゾフェノン、ジエチルチオキサントン、イソプロピルチオキサントン等が例示される。更に、場合によっては、重合開始剤としてアゾ系重合開始剤を併用してもよい。具体的には、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]或いはその二塩酸塩又はその二酢酸塩、2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド]、2,2’-アゾビスイソブチル酸ジメチルエステル、4,4’-アゾビス(4-シアノバレリン酸)或いはその二ナトリウム塩又はその二カリウム塩などが例示される。これらアゾ系化合物は2種以上を併用することが出来る。アゾ系化合物の使用量は、単量体100質量%に対し、通常1質量%以下が好ましく、0.5質量%以下がより好ましく、0.2質量%以下がさらに好ましい。また、通常0.001質量%以上が好ましく、0.002質量%以上がより好ましく、0.005質量%以上がさらに好ましい。具体的には、0.001~1質量%が好ましく、0.002~0.5質量%がより好ましく、0.005~0.2質量%がさらに好ましい。
上記で得られた含水ゲル粒状物は、含水率が5~30質量%となるまで乾燥することが出来る。ここでの含水率は、含水ゲル粒状物の総質量に対する、含水ゲル粒状物中の水の量を意味する。乾燥機としては、公知の種々の装置、例えば、バンド乾燥機、振動流動乾燥機、ディスク乾燥機、コニカル乾燥機などが使用される。乾燥条件は適宜選択することが出来るが、温度が低すぎると乾燥効率が悪く、温度が高すぎると重合体劣化の原因となる。また、乾燥温度を上げることで、加水分解した際に不溶化の原因となるアルデヒド類が増加することが分かっている。中でもα,β-不飽和アルデヒド(以下、「不飽和アルデヒド」ともいう)の増加が著しい。ここで「α,β-不飽和アルデヒド」とは、分子内に不飽和結合とアルデヒド基を含むものを言い、具体的には、クロトンアルデヒド、2,4-ヘキサジエナール(ソルビンアルデヒド)、桂皮アルデヒド、などが挙げられる。従って乾燥温度は、重合体の温度が、通常40℃以上が好ましく、50℃以上がより好ましく、60℃以上がさらに好ましい。また、通常105℃以下が好ましく、100℃以下がより好ましく、100℃以下がさらに好ましい。より具体的には、40~105℃が好ましく、50~100℃がより好ましく、60~100℃がさらに好ましい。乾燥した重合体は公知の方法で粉体化することが出来る。粉体化する方法としては、ウィレー型粉砕機、ボールミル型粉砕機、ハンマーミル型粉砕機などを用いる方法が挙げられる。粉体の粒度は任意に定めうるが、大きすぎると溶解に時間がかかり、小さすぎると溶解時にいわゆるママコの発生や微粉による作業環境の悪化の原因となるので好ましくない。粉体は、篩の目で4メッシュを通過する大きさが好ましく、10メッシュを通過する大きさがより好ましい。また500メッシュに残る大きさが好ましく、100メッシュに残る大きさがより好ましい。前記粉体としては、篩の目で4メッシュを通過し、500メッシュに残る大きさのものが、粉体総重量の80%以上を占めることが好ましく、90%以上を占めることがより好ましい。より具体的には、乾燥後の粉体の平均粒子径は、0.25~5mmが好ましく、0.25~2mmがより好ましい。なお、平均粒子径は以下の方法で測定することができる。
(平均粒子径の測定)
目開き(単位:μm)1700、1000、710、500、250、75の各標準篩と受け皿の重量を測定し、それらを重ね合わせ、粉体状の重合体10gを最上段の篩上に投入した。次いで、電磁振動式篩分器にセットし、5分間振動させ、それぞれの篩と受け皿の重量を測定し、各重量差を求め、それぞれの篩上に残った重合体の割合を算出した。この粒度分布から積算分布曲線を求め、50%の積算値における粒径値を平均粒子径とした。
得られた粉体状N-ビニルカルボン酸アミド(共)重合体中のα,β-不飽和アルデヒドの含有量は、前記重合体に対して0.05質量%以下であることが好ましく、0.03質量%以下であることがより好ましい。0.05質量%より多いと、後述する不溶化防止剤の添加量が増大するため、経済性が悪い。
本発明の第二の態様におけるビニルアミン(共)重合体の製造方法は、架橋結合を有するN-ビニルカルボン酸アミド(共)重合体を加水分解し、ビニルアミン(共)重合体を製造する方法であって、前記加水分解により前記架橋結合の少なくとも一部が切断されるビニルアミン(共)重合体の製造方法である。
本発明の第一の態様における架橋結合を有するN-ビニルカルボン酸アミド(共)重合体は、一部又は全部を加水分解して製紙薬剤や凝集剤用途に好適であるビニルアミン(共)重合体となる。加水分解工程においては酸又は塩基との接触により架橋結合を有するN-ビニルカルボン酸アミド重合体がビニルアミン(共)重合体に変換され、また架橋結合の少なくとも一部が切断される。「架橋結合の少なくとも一部が切断される」とは、架橋結合に含まれるアミド結合又はエステル結合が加水分解されることを意味する。また、架橋構造中の全てのアミド結合又はエステル結合が加水分解されなくてもよく、一部のアミド結合又はエステル結合が加水分解されてもよい。加水分解される架橋結合のアミド結合又はエステル結合は、架橋結合に含まれるアミド結合又はエステル結合の全モル数に対し、80~100モル%であることが好ましく、90~100モル%であることがより好ましい。
また、N-ビニルカルボン酸アミド単位は、全てのアミド結合が加水分解されなくてもよく、一部のアミド結合が加水分解されてもよい。加水分解されるN-ビニルカルボン酸アミド単位は、全N-ビニルカルボン酸アミド単位に対し、10~100モル%であることが好ましく、10~90モル%であることがより好ましい。加水分解の方法としては、架橋結合を有するN-ビニルカルボン酸アミド重合体を乾燥し、粉体状としたものを酸又は塩基存在下に水中に懸濁させて加水分解する方法、架橋結合を有するN-ビニルカルボン酸アミド重合体の塊状ゲルを解砕して粒状物となし、前記粒状物に酸又は塩基を混合し加水分解する方法、架橋結合を有するN-ビニルカルボン酸アミド重合体を炭化水素系分散媒中に油中水型で分散し、酸又は塩基を添加することで加水分解する方法などが挙げられるが、均一な加水分解を行うため、酸又は塩基存在下に、水中に懸濁させて反応を行うことが好適である。また生産性、輸送性を高めるために、なるべくポリマー濃度(N-ビニルカルボン酸アミド重合体の濃度)の高い条件で反応を行うことが望ましい。ポリマー濃度は溶解装置の能力と経済性との兼ね合いで決められるが、通常は酸又は塩基存在下に水中に懸濁させる場合、懸濁液の総質量に対し、0.1重量%以上が好ましく、1重量%以上がより好ましく、2重量%以上がさらに好ましい。また、通常は30重量%以下が好ましく、20重量%以下がより好ましく、15重量%以下がさらに好ましい。より具体的には、0.1~30重量%以下が好ましく、1~20重量%がより好ましく、2~15重量%がさらに好ましい。油中水型で分散させた分散液の場合、分散液の総質量に対し、ポリマー濃度は好ましくは0.1~50重量%であり、より好ましくは5~40重量%である。
不溶化防止剤の使用量は、N-ビニルカルボン酸アミド重合体中に残存する単量体量、あるいは不純物として存在するアルデヒド類の量によって異なるが、重合体100質量部に対し、通常0.1質量部以上が好ましく、0.2質量部以上がより好ましい。また、通常10質量部以下が好ましく、4質量部以下がより好ましい。具体的には、重合体100質量部に対し、0.1~10質量部が好ましく、0.2~4質量部がより好ましい。不溶化防止剤は、重合体粉末の溶解後に添加してもよく、重合体粉末を溶解させる水に予め添加しておいてもよい。また含水ゲルや重合体粉末に対して添加してもよい。
上記のようにして得た架橋結合を有するN-ビニルカルボン酸アミド(共)重合体溶液は、加熱することによって加水分解を促進することができる。加水分解温度は、30℃ 以上が好ましく、50℃以上がより好ましく、60℃以上がさらに好ましい。また、180℃ 以下が好ましく、140℃以下がより好ましく、100℃以下がさらに好ましい。より具体的には、30~180℃が好ましく、50~140℃がより好ましく、60~100℃がさらに好ましい。低すぎる温度で加水分解を行うと、架橋結合の少なくとも一部の切断に時間を要し、均一な水溶液とならないため、加水分解にムラが生じてしまう。一方、高すぎる温度で加水分解を行うと、重合体の劣化を促進するおそれがある。加熱時間は所望の加水分解率に応じて定めればよいが、高温で長時間加熱すると劣化を促進するおそれがあるので48時間以内が望ましく、好ましくは24時間以内、さらに好ましくは12時間以内である。加水分解の条件によっては加水分解に用いた酸又は塩基がビニルアミン(共)重合体に残存している場合がある。これらの残存した酸又は塩基は必要に応じて中和してもよい。
加水分解に好適な酸は、例えば、無機酸の中では、例えば、ハロゲン化水素(水溶液中では塩酸)、硫酸、硝酸、燐酸、(オルト-、メタ-ポリ燐酸)である。有機酸の中では、例えば、蟻酸、酢酸、プロピオン酸などの炭素数1~5のカルボン酸、あるいは、メタンスルホン酸、ベンゼンスルホン酸、トルエンスルホン酸などの脂肪族又は芳香族スルホン酸である。これらの中では塩酸が好ましい。
酸又は塩基の使用量は、所望する加水分解率によって異なるが、目的とするビニルアミン(共)重合体の製造で使用したN-ビニルカルボン酸アミドと共重合した架橋剤とを合計した添加量に対し、通常0.8倍モル当量以上が好ましく、1倍モル当量以上がより好ましい。また、通常2倍モル当量以下が好ましく、1.5倍モル当量以下がより好ましい。具体的には、0.8~2倍モル当量が好ましく、1~1.5倍モル当量がより好ましい。また、酸又は塩基は、予め溶解して溶液として加水分解反応に供するのが好ましい。その場合、溶液の濃度は高い方が反応操作上好ましい。加水分解率は、N-ビニルカルボン酸アミド単量体単位に対する割合として、通常0.1モル%以上が好ましく、1モル%以上がより好ましい。また、通常100モル%以下が好ましく、95モル%以下がより好ましい。より具体的には、0.1~100モル%が好ましく、1~95モル%がさらに好ましい。
本発明の第三の態様におけるビニルアミン(共)重合体は、N-ビニルカルボン酸アミド(共)重合体を加水分解して得られる。ビニルアミン(共)重合体は、ビニルアミン単位を含む(共)重合体であり、水溶性である。また、架橋剤単位であて、架橋剤単位中の一部の構造(アミド結合又はエステル結合)が加水分解されてカルボキシル基又はヒドロキシル基に変換された架橋剤単位を含む。
ビニルアミン単位は、ビニルアミン(共)重合体を構成する全構成単位に対し、9.5~99.9モル%であることが好ましく、10~90モル%であることがより好ましい。
架橋剤単位のうち、加水分解された架橋剤単位は、全架橋剤単位に対して80~100モル%であることが好ましく、90~100モル%であることがより好ましい。
還元粘度は以下の方法で測定することができる。
(還元粘度の測定)
ビニルアミン(共)重合体水溶液を1規定の食塩水中に、純分0.1g/dLの濃度に溶解してサンプル溶液とし、25℃において、オストワルド粘度計を用いて流下時間を測定する。同様に、1規定食塩水の流下時間を測定し、次式によって還元粘度を求める。
[数1]
還元粘度 ηsp/C = (t-t0)/t0/0.1 [dL/g]
t:サンプル溶液の流下時間(秒)
t0:1規定食塩水の流下時間(秒)
N-ビニルカルボン酸アミド(共)重合体の塊状ゲル片を3cm角以下に切断した後にダイスの穴径が4.8mmのミートチョッパーで処理する。ダイスを通過して得られるゲルの形状からゲルの取り扱い性を以下の2段階で評価し、ゲルの取り扱い性とした。
○:ゲルが細粒化されたままの形状を保持しており取り扱い性に優れる
×:細粒化後に大半のゲル粒子が合着し、ストランド状になるため取り扱いが困難になる
加水分解後のビニルアミン(共)重合体水溶液を1規定の食塩水中に、純分0.1g/dLの濃度に溶解してサンプル溶液とし、25℃において、オストワルド粘度計を用いて流下時間を測定した。同様に、1規定食塩水の流下時間を測定し、次式によって還元粘度を求めた。
[数2]
還元粘度 ηsp/C = (t-t0)/t0/0.1 [dL/g]
t:サンプル溶液の流下時間(秒)
t0:1規定食塩水の流下時間(秒)
N-ビニルカルボン酸アミド(共)重合体、又はビニルアミン(共)重合体を1質量%となるよう脱塩水を加え水溶液全量を500gとし、280回転/分で1時間攪拌した後、水溶液を目開き180μmの金網を通して濾過し、金網上の残物を水道水で洗浄した。金網上の残物である不溶解ゲル分の重量を測定した。
N-ビニルカルボン酸アミド(共)重合体2gを三角フラスコに分取し、そこにメタノールを20ml添加した。室温で5時間攪拌を行い、重合体とメタノールをろ紙にて分離した。分離したメタノールに、溶液のpHが1となるよう35%塩酸水溶液を添加し、2,4-ジニトロフェニルヒドラジンを0.01g添加した。この混合溶液を45℃で1時間反応させ、超純水45体積%/アセトニトリル55体積%の水溶液で10倍に希釈した。前記反応により生成した前記希釈溶液中の誘導体を、以下の分析条件にて、液体クロマトグラフフィーにより絶対検量線法で定量分析することにより前記不飽和アルデヒド含有量を算出した。
分析システム:島津LC分析システム
カラム:ODPカラム(Shodex ODP 4.6mm×250mmH)
溶離液:超純水45体積%/アセトニトリル55体積%
流速:1ml/min
分析温度:40℃
サンプル注入量:20μl
検出器:UV検出器(波長360nm)
脱イオン水68重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、連鎖移動剤としてホスフィン酸ナトリウム0.5質量%(対単量体)を溶解し、ついでN-ビニルホルムアミド(純度99質量%)32重量部を混合した。得られた単量体水溶液に、原料単量体に対して7質量%のポリエチレングリコール♯600ジアクリレート(商品名:新中村化学工業製 NKエステル A-600)を溶解した後、リン酸により単量体水溶液がpH6.3となるように調整し、単量体調整液を得た。
ポリエチレングリコール♯600ジアクリレートをポリエチレングリコール♯600ジメタクリレート(商品名:新中村化学工業製 NKエステル 14G)に変更した以外は実施例1と同様の操作を行い、N-ビニルホルムアミド(共)重合体を得たが、得られたゲル粒状物は、細粒の形状を維持し、取り扱い性も良好であった。
次に、実施例1と同様の方法で加水分解を行い、全N-ビニルホルムアミド単位中、40モル%がビニルアミン単位に変換されたビニルアミン(共)重合体水溶液(濃度10質量%)を得た。この水溶液を1質量%に希釈溶解し、不溶解分測定を行った。なお得られたビニルアミン(共)重合体の還元粘度は0.6dL/gであった。結果を表1に示す。
ポリエチレングリコール♯600ジアクリレートをアジピン酸ジビニルに変更した以外は実施例1と同様の操作を行い、N-ビニルホルムアミド(共)重合体を得たが、得られたゲル粒状物は、細粒の形状を維持し、取り扱い性も良好であった。
次に、実施例1と同様の方法で加水分解を行い、全N-ビニルホルムアミド単位中、40モル%がビニルアミン単位に変換されたビニルアミン(共)重合体水溶液(濃度10質量%)を得た。この水溶液を1質量%に希釈溶解し、不溶解分測定を行った。なお得られたビニルアミン(共)重合体の還元粘度は0.6dL/gであった。結果を表1に示す。
脱イオン水50質量部にN-ビニルホルムアミド(純度99質量%)50質量部を混合し、得られた単量体水溶液に、単量体に対して0.2質量%のポリエチレングリコール♯600ジアクリレート(商品名:新中村化学工業製 NKエステル A-600)を溶解した後、リン酸により単量体水溶液がpH6.3となるように調整し、単量体調整液を得た。
この単量体調整液に連鎖移動剤としてホスフィン酸ナトリウム10質量%水溶液0.5質量%(対単量体)と光重合開始剤D4265(チバスペシャリティケミカル製)を0.4質量%(対単量体)加えて10℃まで冷却しながら20分間窒素曝気を行い、溶存酸素を除去した。
底面がステンレス製のトレー状容器(底面200mm×200mm)の底面に、ポリエチレンテレフタレートフィルム[ベースフィルム12μm厚、PVDC(ポリビニリデンクロライド)コート4μm厚]を敷き、ここに前記単量体調整液を液の厚さが10mmになる分量を入れ、上部をポリエチレンテレフタレートフィルムでカバーした。上方より蛍光ケミカルランプを照射面で10W/m2の強度になるように照射した。照射期間中は、容器のステンレス面に10℃の冷水を噴霧して重合熱を除熱した。反応開始から60分後に冷水の噴霧を停止してから照射強度を20W/m2に上げ、さらに90分間重合を継続した。重合温度の最高点は照射開始から85分後に観測された。合計150分間の光重合終了後に反応容器より生成重合体を取り出し、重合体ゲルを得た。
前記重合体ゲルを2cm角片に解砕し、解砕されたゲル片をダイスの穴径が4.8mmのミートチョッパーで処理し、ゲル片を5mm角以下に小粒化された粒状物とした。得られたゲル粒状物は、細粒の形状を維持し、取り扱い性も良好であった。次いで、105℃の通風乾燥機でゲル粒状物を1.5時間乾燥し、その後粉砕し粉体とした。
次に、実施例1と同様の方法で加水分解を行い、全N-ビニルホルムアミド単位中、40モル%がビニルアミン単位に変換されたビニルアミン(共)重合体水溶液(濃度10質量%)を得た。この水溶液を1質量%に希釈溶解し、不溶解分測定を行った。なお得られたビニルアミン(共)重合体の還元粘度は0.5dL/gであった。結果を表1に示す。
実施例1において、純度99%のN-ビニルホルムアミドから、純度92%のN-ビニルホルムアミドに変更し、実施例1に記載の開始剤に加え、硫酸第一鉄0.03質量%(対単量体)を5質量%の水溶液として添加したこと以外は実施例1と同様にして重合を実施した。重合開始から150分後に系内温度91℃に達し、低純度のN-ビニルホルムアミドにおいても、十分な重合速度を維持できた。得られたN-ビニルホルムアミド(共)重合体ゲル粒状物は、細粒の形状を維持し、取り扱い性も良好であった。
次に、実施例1と同様の方法で加水分解を行い、全N-ビニルホルムアミド単位中、40モル%がビニルアミン単位に変換されたビニルアミン(共)重合体水溶液(濃度10質量%)を得た。この水溶液を1質量%に希釈溶解し、不溶解分測定を行った。なお得られたビニルアミン(共)重合体の還元粘度は0.5dL/gであった。結果を表1に示す。
ポリエチレングリコール♯600ジアクリレートを添加しないこと以外は実施例1と同様の操作を行い、N-ビニルホルムアミド(共)重合体を得たが、細粒化後に大半のゲル粒子が合着し、ストランド状になったため取り扱いが困難であった。
次に、実施例1と同様の方法で加水分解を行い、全N-ビニルホルムアミド単位中、40モル%がビニルアミン単位に変換されたビニルアミン(共)重合体水溶液(濃度10質量%)を得た。この水溶液を1質量%に希釈溶解し、不溶解分測定を行った。なお得られたビニルアミン(共)重合体の還元粘度は0.6dL/gであった。結果を表1に示す。
ポリエチレングリコール♯600ジアクリレートを添加しないこと以外は実施例2と同様の操作を行い、N-ビニルホルムアミド(共)重合体を得たが、細粒化後に大半のゲル粒子が合着し、ストランド状になったため取り扱いが困難であった。
実施例1と同様の操作を行い、N-ビニルホルムアミド(共)重合体を得た。得られたゲル粒状物は、細粒の形状を維持し、取り扱い性も良好であった。
ポリエチレングリコールジアクリレートをテトラアリルオキシエタンに変更した以外は実施例1と同様の操作を行い、N-ビニルホルムアミド(共)重合体を得たが、得られたゲル粒状物は、細粒の形状を維持し、取り扱い性も良好であった。
Claims (15)
- 架橋結合を有する水不溶性のN-ビニルカルボン酸アミド(共)重合体であって、前記N-ビニルカルボン酸アミド(共)重合体を加水分解して得られるビニルアミン(共)重合体が水溶性である、N-ビニルカルボン酸アミド(共)重合体。
- 前記架橋結合が多官能(メタ)アクリレート単位を含む架橋結合である、請求項1に記載のN-ビニルカルボン酸アミド(共)重合体。
- 前記架橋結合がN-ビニルカルボン酸アミド(共)重合体100質量%に対し、0.1~15質量%である、請求項1又は2に記載のN-ビニルカルボン酸アミド(共)重合体。
- 前記N-ビニルカルボン酸アミド(共)重合体を加水分解して得られるビニルアミン(共)重合体を0.1g/dL含む1mol/L塩化ナトリウム水溶液の25℃における還元粘度が、0.1~10dl/gである、請求項1~3のいずれか一項に記載のN-ビニルカルボン酸アミド(共)重合体。
- 前記N-ビニルカルボン酸アミド(共)重合体がN-ビニルホルムアミド(共)重合体である、請求項1~4のいずれか一項に記載のN-ビニルカルボン酸アミド(共)重合体。
- 架橋結合を有するN-ビニルカルボン酸アミド(共)重合体を加水分解し、ビニルアミン(共)重合体を得るビニルアミン(共)重合体の製造方法であって、前記加水分解により前記架橋結合の少なくとも一部が切断されるビニルアミン(共)重合体の製造方法。
- 前記架橋結合が多官能(メタ)アクリレートを架橋剤として、N-ビニルカルボン酸アミドと重合させることにより形成される、請求項6に記載の製造方法。
- 前記N-ビニルカルボン酸アミド(共)重合体が水不溶性であり、得られるビニルアミン(共)重合体が水溶性である、請求項6又は7に記載の製造方法。
- 前記N-ビニルカルボン酸アミド(共)重合体がN-ビニルホルムアミド(共)重合体である、請求項6~8のいずれか一項に記載の製造方法。
- 前記N-ビニルカルボン酸アミド(共)重合体が断熱重合法又は光重合法により得られるN-ビニルカルボン酸アミド(共)重合体である、請求項6~9のいずれか一項に記載の製造方法。
- 前記N-ビニルカルボン酸アミド(共)重合体が重合開始剤として硫酸第一鉄を用いた断熱重合により得られるN-ビニルカルボン酸アミド(共)重合体である、請求項6~10のいずれか一項に記載の製造方法。
- 前記N-ビニルカルボン酸アミド(共)重合体の原料単量体100質量%に対し、多官能(メタ)アクリレートを0.1~15質量%使用する、請求項7に記載の製造方法。
- 加水分解の前に、前記N-ビニルカルボン酸アミド(共)重合体を105℃以下で乾燥したのち粉砕して粉体とする、請求項6~12のいずれか一項に記載の製造方法。
- 前記N-ビニルカルボン酸アミド(共)重合体中の不飽和アルデヒドの含有量が、前記N-ビニルカルボン酸アミド(共)重合体100質量%に対して0.05質量%以下である、請求項6~13のいずれか一項に記載の製造方法。
- 加水分解を強酸又は強塩基の存在下に行う、請求項6~14のいずれか一項に記載の製造方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014556846A JPWO2015068806A1 (ja) | 2013-11-08 | 2014-11-07 | ビニルアミン(共)重合体の製造方法 |
CA2927284A CA2927284A1 (en) | 2013-11-08 | 2014-11-07 | Method for producing vinylamine (co)polymer |
CN201480057039.5A CN105658681B (zh) | 2013-11-08 | 2014-11-07 | 乙烯基胺聚合物的制造方法 |
US15/030,280 US20160237191A1 (en) | 2013-11-08 | 2014-11-07 | Method for producing vinylamine (co)polymer |
KR1020167010149A KR20160058162A (ko) | 2013-11-08 | 2014-11-07 | 비닐아민 (공)중합체의 제조 방법 |
EP14860710.4A EP3067373B1 (en) | 2013-11-08 | 2014-11-07 | Method for producing vinylamine (co)polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013231762 | 2013-11-08 | ||
JP2013-231762 | 2013-11-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015068806A1 true WO2015068806A1 (ja) | 2015-05-14 |
Family
ID=53041581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/079590 WO2015068806A1 (ja) | 2013-11-08 | 2014-11-07 | ビニルアミン(共)重合体の製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20160237191A1 (ja) |
EP (1) | EP3067373B1 (ja) |
JP (1) | JPWO2015068806A1 (ja) |
KR (1) | KR20160058162A (ja) |
CN (1) | CN105658681B (ja) |
CA (1) | CA2927284A1 (ja) |
WO (1) | WO2015068806A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111019043B (zh) * | 2019-12-12 | 2021-07-13 | 贵州师范学院 | 一种co2/n2开关型温敏聚合物及其制备方法 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6151007A (ja) * | 1984-08-20 | 1986-03-13 | Mitsubishi Chem Ind Ltd | ポリビニルアミン架橋物の製造方法 |
JPS61118406A (ja) | 1984-11-14 | 1986-06-05 | Mitsubishi Chem Ind Ltd | 水溶性ポリビニルアミンの製造方法 |
JPH0586127A (ja) | 1991-09-27 | 1993-04-06 | Mitsubishi Kasei Corp | 水溶性ポリマーの製造法 |
JPH0597931A (ja) | 1991-10-08 | 1993-04-20 | Mitsubishi Kasei Corp | N−ビニルカルボン酸アミド重合体の製造法 |
JPH05125109A (ja) | 1990-03-08 | 1993-05-21 | Basf Ag | N−ビニルホルムアミドの加水分解された粉末状重合体の製法及び製紙用の脱水剤、保持剤及び凝結剤 |
JP2000017026A (ja) | 1998-07-01 | 2000-01-18 | Sekisui Plastics Co Ltd | N−ビニルカルボン酸アミド系架橋共重合樹脂およびその製造方法 |
WO2000058378A1 (fr) | 1999-03-29 | 2000-10-05 | Snf S.A. | Nouveaux procedes de synthese d'agents floculants et coagulants de type polyvinylamine pva, nouveaux agents obtenus, leurs utilisations, et papiers ameliores ainsi obtenus |
JP2002145963A (ja) * | 2000-11-09 | 2002-05-22 | Daiyanitorikkusu Kk | N−ビニルカルボン酸アミド系共重合体の製造方法および得られたn−ビニルカルボン酸アミド系共重合体の用途 |
JP2003512608A (ja) * | 1999-10-19 | 2003-04-02 | アメルシャム・バイオサイエンシーズ・アクチボラグ | 分離用ゲルの製造のための方法およびキット |
JP3704660B2 (ja) | 2001-11-14 | 2005-10-12 | ダイヤニトリックス株式会社 | ポリビニルアミンの製造方法 |
JP2008183541A (ja) * | 2007-01-31 | 2008-08-14 | Sanyo Chem Ind Ltd | 高分子凝集剤 |
JP2009179724A (ja) | 2008-01-31 | 2009-08-13 | Toray Ind Inc | 架橋ポリビニルアミン又はその酸付加塩、及びその医薬用途 |
JP2010059220A (ja) | 2008-09-01 | 2010-03-18 | Daiyanitorikkusu Kk | N−ビニルカルボン酸アミド系重合体の製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2310675A1 (en) * | 1997-11-19 | 1999-05-27 | Thomas W. Beihoffer | Poly(vinylamine)-based superabsorbent gels and method of manufacturing the same |
US5981689A (en) * | 1997-11-19 | 1999-11-09 | Amcol International Corporation | Poly(vinylamine)-based superabsorbent gels and method of manufacturing the same |
DE102005053559A1 (de) * | 2005-11-08 | 2007-05-10 | Basf Ag | Verfahren zur Herstellung von Vinylformamid-Einheiten enthaltenden Polymerpulvern |
-
2014
- 2014-11-07 US US15/030,280 patent/US20160237191A1/en not_active Abandoned
- 2014-11-07 CA CA2927284A patent/CA2927284A1/en not_active Abandoned
- 2014-11-07 CN CN201480057039.5A patent/CN105658681B/zh not_active Expired - Fee Related
- 2014-11-07 EP EP14860710.4A patent/EP3067373B1/en not_active Not-in-force
- 2014-11-07 WO PCT/JP2014/079590 patent/WO2015068806A1/ja active Application Filing
- 2014-11-07 JP JP2014556846A patent/JPWO2015068806A1/ja active Pending
- 2014-11-07 KR KR1020167010149A patent/KR20160058162A/ko not_active Application Discontinuation
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6151007A (ja) * | 1984-08-20 | 1986-03-13 | Mitsubishi Chem Ind Ltd | ポリビニルアミン架橋物の製造方法 |
JPS61118406A (ja) | 1984-11-14 | 1986-06-05 | Mitsubishi Chem Ind Ltd | 水溶性ポリビニルアミンの製造方法 |
JPH05125109A (ja) | 1990-03-08 | 1993-05-21 | Basf Ag | N−ビニルホルムアミドの加水分解された粉末状重合体の製法及び製紙用の脱水剤、保持剤及び凝結剤 |
JPH0586127A (ja) | 1991-09-27 | 1993-04-06 | Mitsubishi Kasei Corp | 水溶性ポリマーの製造法 |
JPH0597931A (ja) | 1991-10-08 | 1993-04-20 | Mitsubishi Kasei Corp | N−ビニルカルボン酸アミド重合体の製造法 |
JP2000017026A (ja) | 1998-07-01 | 2000-01-18 | Sekisui Plastics Co Ltd | N−ビニルカルボン酸アミド系架橋共重合樹脂およびその製造方法 |
WO2000058378A1 (fr) | 1999-03-29 | 2000-10-05 | Snf S.A. | Nouveaux procedes de synthese d'agents floculants et coagulants de type polyvinylamine pva, nouveaux agents obtenus, leurs utilisations, et papiers ameliores ainsi obtenus |
JP2003512608A (ja) * | 1999-10-19 | 2003-04-02 | アメルシャム・バイオサイエンシーズ・アクチボラグ | 分離用ゲルの製造のための方法およびキット |
JP2002145963A (ja) * | 2000-11-09 | 2002-05-22 | Daiyanitorikkusu Kk | N−ビニルカルボン酸アミド系共重合体の製造方法および得られたn−ビニルカルボン酸アミド系共重合体の用途 |
JP3704660B2 (ja) | 2001-11-14 | 2005-10-12 | ダイヤニトリックス株式会社 | ポリビニルアミンの製造方法 |
JP2008183541A (ja) * | 2007-01-31 | 2008-08-14 | Sanyo Chem Ind Ltd | 高分子凝集剤 |
JP2009179724A (ja) | 2008-01-31 | 2009-08-13 | Toray Ind Inc | 架橋ポリビニルアミン又はその酸付加塩、及びその医薬用途 |
JP2010059220A (ja) | 2008-09-01 | 2010-03-18 | Daiyanitorikkusu Kk | N−ビニルカルボン酸アミド系重合体の製造方法 |
Non-Patent Citations (1)
Title |
---|
JOO-HYUN HAN ET AL.: "A facile approach to synthesize uniform hydrogel shells with controllable loading and releasing properties", CHEMICAL COMMUNICATIONS, no. 8, 2008, pages 984 - 986, XP055279852 * |
Also Published As
Publication number | Publication date |
---|---|
CA2927284A1 (en) | 2015-05-14 |
CN105658681A (zh) | 2016-06-08 |
KR20160058162A (ko) | 2016-05-24 |
US20160237191A1 (en) | 2016-08-18 |
EP3067373A4 (en) | 2016-11-23 |
EP3067373A1 (en) | 2016-09-14 |
JPWO2015068806A1 (ja) | 2017-03-09 |
EP3067373B1 (en) | 2018-06-20 |
CN105658681B (zh) | 2018-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5584962B2 (ja) | N−ビニルカルボン酸アミド系重合体の製造方法 | |
JP3240144B2 (ja) | マルチモードエマルジョン及びマルチモードエマルジョンの製造法 | |
JP4744170B2 (ja) | 水溶性ビニルアミン重合体の製造方法 | |
JP2008156542A (ja) | 水溶性高分子の製造方法 | |
JP6876394B2 (ja) | N−ビニルラクタム系架橋重合体の製造方法及びn−ビニルラクタム系架橋重合体 | |
JP6546188B2 (ja) | 構造化ブロック共重合体 | |
WO2015068806A1 (ja) | ビニルアミン(共)重合体の製造方法 | |
JP2010229362A (ja) | 油中水型マイクロゲルエマルジョン | |
JP5137080B2 (ja) | ポリアミジン系水溶性高分子の製造方法 | |
JP5604891B2 (ja) | 粉体状ポリビニルアミンの製造方法 | |
JP5843426B2 (ja) | N−ビニルホルムアミド重合体の加水分解物を含む組成物及びその製造方法 | |
JP2011153109A (ja) | 不飽和第4級アンモニウム塩化合物からなる帯電防止剤及び帯電防止組成物 | |
CA2943935C (en) | Method for producing vinylamine unit-containing polymer and polymerization product | |
JP3704660B2 (ja) | ポリビニルアミンの製造方法 | |
JP5846731B2 (ja) | ポリビニルアミン又はポリアミジンの製造方法 | |
JP3851232B2 (ja) | ポリビニルアミンの製造方法 | |
JP2004224998A (ja) | アクリルアミド系水溶性重合体の製造方法 | |
JP4449247B2 (ja) | 水溶性重合体の製造方法 | |
JP5461978B2 (ja) | アクリルアミド系水溶性重合体の製造方法 | |
JPH0326206B2 (ja) | ||
JP2004075814A (ja) | N−ビニルカルボン酸アミド重合体の製造方法 | |
JP4992371B2 (ja) | 粉末状カチオン系水溶性高分子化合物の製造方法 | |
JP2007056222A (ja) | アクリル酸(塩)系水溶性重合体の製造方法 | |
JP2008094931A (ja) | 粉末状両性系水溶性高分子化合物の製造方法 | |
JP2009079135A (ja) | 水溶性重合体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2014556846 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14860710 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2927284 Country of ref document: CA |
|
REEP | Request for entry into the european phase |
Ref document number: 2014860710 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15030280 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20167010149 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |