WO2011148862A1 - ジアリルアミン類と二酸化硫黄との共重合体の製造方法 - Google Patents
ジアリルアミン類と二酸化硫黄との共重合体の製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/205—Copolymers of sulfur dioxide with unsaturated organic compounds
- C08G75/22—Copolymers of sulfur dioxide with unsaturated aliphatic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
- C08G2650/24—Polymeric initiators
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- the present invention relates to a method for producing a copolymer of diallylamines and sulfur dioxide, and more specifically, a copolymer of diallylamines and sulfur dioxide, which can produce a copolymer having a higher molecular weight than conventional methods. It relates to a manufacturing method.
- a copolymer of diallylamines and sulfur dioxide can be produced in high yield by copolymerizing diallylamines and sulfur dioxide in a polar solvent in the presence of a radical polymerization initiator (for example, Patent Document 1). Or 2).
- the copolymer of diallylamines and sulfur dioxide obtained by this production method is water-soluble, and it has been proposed to be used in various fields such as water-soluble paints and dyeing fastness improvers for dyed products (for example, , See Patent Document 1).
- Patent Document 1 the conventional production method described in Patent Document 1 generally provides only a low molecular weight copolymer, and a copolymer of a high molecular weight diallylamine and sulfur dioxide is obtained. It was difficult to manufacture. Moreover, it is not easy to control the molecular weight of the produced copolymer depending on the monomer concentration, the amount of radical polymerization initiator to be added, and the like.
- the object of the present invention is to produce a copolymer having a higher molecular weight than that of the conventional method, in particular, a copolymer having a high molecular weight and water solubility.
- An object of the present invention is to provide a method for producing a copolymer of diallylamines and sulfur dioxide, the molecular weight of which can be controlled.
- the present invention provides a method for producing a copolymer of diallylamines and sulfur dioxide, which can produce a copolymer having a higher molecular weight than that of the conventional method and water-soluble. Consists of the following [1] to [5]. [1]. In the presence of an acid and a radical polymerization initiator in a polar solvent, the following general formula (I) (Wherein R 1 and R 2 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X a- represents a counter ion, and a represents a valence of the counter ion).
- a method for producing a copolymer of diallylamines and sulfur dioxide characterized by copolymerizing thiols and sulfur dioxide. [2].
- the diallylamine (I) and the acid are mixed in a polar solvent, and then the resulting acidic solution of the diallylamine (I) is mixed with sulfur dioxide. In the resulting mixture, the presence of a radical polymerization initiator is present.
- the method according to [1], wherein the diallylamine (I) and sulfur dioxide are copolymerized below. [3].
- diallylamines (I) are diallylamines selected from the group consisting of diallyldimethylammonium chloride, diallylethylmethylammonium ethyl sulfate, diallylmethylamine hydrochloride and diallylamine hydrochloride.
- the method described in 1. [5]. The method according to any one of [1] to [4], wherein the produced copolymer of diallylamine (I) and sulfur dioxide has a molecular weight of 2,800 to 200,000.
- a copolymer of diallylamines and sulfur dioxide which has a higher molecular weight than that of the conventional method and is water-soluble, can be produced in a high yield. Moreover, it is possible to control the molecular weight of the copolymer obtained by selecting the kind and amount of the acid used in the method of the present invention.
- FIG. 1 is a diagram showing an IR spectrum of a copolymer of diallyldimethylammonium chloride and sulfur dioxide obtained in Example 1.
- FIG. 1 is a diagram showing a GPC chart of a copolymer of diallyldimethylammonium chloride and sulfur dioxide obtained in Example 1.
- FIG. 1 is a diagram showing a GPC chart of a copolymer of diallyldimethylammonium chloride and sulfur dioxide obtained in Example 1.
- diallylamines used as a raw material monomer in the method for producing a copolymer of diallylamines of the present invention and sulfur dioxide (hereinafter sometimes referred to as SO 2 in this specification) are represented by the following general formula (I): It is represented by
- R 1 and R 2 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and the provir group and the butyl group may be linear or branched.
- X a- represents a counter ion, and examples include chlorine ion, bromine ion, iodine ion, sulfate ion, carboxylate ion, dicarboxylate ion, phosphate ion, alkylsulfonate ion, sulfamate ion, and hydroxide ion. it can.
- A represents the valence of the counter ion.
- R 1 and / or R 2 is a hydrogen atom and X a ⁇ is a hydroxide ion
- the diallylamines represented by the general formula (I) are in a free form without ions.
- diallylamines used in the method of the present invention include diallyldialkylammonium salts, diallylalkylamine salts, diallylamine salts and the like.
- diallyldialkylammonium salts include diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium iodide, diallyldimethylammonium methylsulfate, diallyldimethylammonium ethylsulfate, diallylethylmethylammonium chloride, diallylethylmethylammonium bromide, diallyl Ethyl methyl ammonium iodide, diallyl ethyl methyl ammonium methyl sulfate, diallyl ethyl methyl ammonium ethyl sulfate, diallyl diethyl ammonium chloride, diallyl diethyl ammonium bromide, dially
- diallylalkylamine salts include diallylmethylamine hydrochloride, diallylmethylamine hydrobromide, diallylmethylamine hydroiodide, diallylmethylamine sulfate, diallylmethylamine methanesulfonate, diallylethylamine hydrochloride Salt, diallylethylamine hydrobromide, diallylethylamine hydroiodide, diallylethylamine sulfate, diallylethylamine methanesulfonate, diallylpropylamine hydrochloride, diallylpropylamine hydrobromide, diallylpropylamine iodide Mention may be made of hydrogenates, diallylpropylamine sulfate, diallylpropylamine methanesulfonate.
- diallylamine salts include diallylamine hydrochloride, diallylamine hydrobromide, diallylamine hydroiodide, diallylamine sulfate, and diallylamine methanesulfonate.
- diallyldimethylammonium chloride hereinafter sometimes referred to as DADMAC
- diallylethylmethylammonium ethyl sulfate hereinafter sometimes referred to as DAEMAES
- diallylmethyl Amine hydrochloride hereinafter also referred to as DAMA-HCl in the present specification
- DAA-HCl diallylamine hydrochloride
- these 1 type may be used independently or may be used in combination of 2 or more type.
- the concentration of the total monomer in the reaction mixture of the amount of diallylamines and the amount of sulfur dioxide is preferably 40.00 to 80.00% by mass, and 45.00 to 78.78. 00 mass% is preferable, 50.00 to 76.00 mass% is more preferable, 55.00 to 74.00 mass% is further more preferable, and 60.00 to 72.00 mass% is particularly preferable.
- the charged monomer molar ratio of diallylamines / sulfur dioxide is usually 0.5 / 0.5 or more, preferably 0.5, from the viewpoint of the stability of the resulting copolymer. /0.5 to 0.95 / 0.05, more preferably 0.5 / 0.5 to 0.8 / 0.2, still more preferably 0.5 / 0.5 to 0.6. /0.4, particularly preferably 0.5 / 0.5.
- the acid used in the method of the present invention may be an organic acid or an inorganic acid, but for example, an acid having a pKa of 4.0 or less, preferably an acid having a pKa of 2.0 or less, more preferably a pKa of 1
- the smaller the pKa value of the acid used the higher the molecular weight of the copolymer of diallylamines and sulfur dioxide obtained in the method of the present invention.
- pKa indicates the ionization index of the acid, and is an equilibrium constant that varies depending on temperature and ionic strength.
- the pKa value of the acid used in the method of the present invention the pKa value described in Chemical Handbook Basic Revised Edition 5 (Maruzen Co., Ltd.) can be used.
- the pKa value of acid means the pKa value in water at 25 ° C.
- the pKa value of the acid means the pKa value at 25 ° C.
- the pKa value of the acid was adjusted to 0.1 mol / l ionic strength using ultrapure water substituted with nitrogen at 25 ° C.
- An aqueous solution is prepared, and the pKa value of this aqueous solution can be determined by measuring with a potentiometric titrator, for example, AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.
- the pKa of the acid used in the method of the present invention means pKa (pKa1) in the first-stage dissociation reaction.
- Examples of the acid used in the method of the present invention include hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, chlorosulfuric acid, fluorosulfuric acid, amidosulfuric acid, sulfuric acid, phosphoric acid, perchloric acid, and methanesulfonic acid.
- Ethanesulfonic acid propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, trifluoroacetic acid, trichloroacetic acid, and hydroxyacetic acid.
- hydrochloric acid or sulfuric acid is preferable because a copolymer of high molecular weight diallylamines and sulfur dioxide can be obtained.
- the amount of acid used in the method of the present invention is, for example, 4 to 48 mol%, preferably 5 to 40 mol%, more preferably 6 to 35 mol%, based on the total moles of all monomers. 7 to 33 mol% is more preferable, and 8 to 32 mol% is particularly preferable.
- diallylamines may be mixed with the acid in a polar solvent, and the diallylamines and sulfur dioxide are mixed in the polar solvent. After mixing, the reaction solution and the acid may be mixed. However, from the viewpoint of ease of production operation, it is preferable to mix the diallylamine salt with the acid in a polar solvent and then mix the reaction solution with sulfur dioxide. .
- an acidic solution of diallylamines obtained by mixing diallylamines and an acid in a polar solvent has, for example, a pH of 3.30 or less and preferably a pH of 2.00 or less.
- the pH is more preferably 1.35 or less, the pH is further preferably 0.80 or less, and the pH is particularly preferably 0.40 or less.
- the pH of the acidic solution of diallylamines is preferably 1.35 or less, and 1.00 Or less, more preferably 0.80 or less, and particularly preferably 0.40 or less.
- the pH value in the present invention is a value measured with a pH meter, for example, pH METER F-22 manufactured by HORIBA under the condition of 25 ° C.
- radical polymerization initiator used in the method of the present invention examples include organic peroxides such as tertiary-butyl hydroperoxide and cumene hydroperoxide, and aliphatic azo such as 2,2′-azobisisobutyronitrile.
- examples thereof include compounds, inorganic peroxides such as ammonium persulfate and potassium persulfate, and nitrates such as ammonium nitrate and potassium nitrate.
- the gas containing oxygen such as air, a radiation, an ultraviolet-ray, and visible light are also mentioned.
- the amount and use method of the radical polymerization initiator are not particularly limited. For example, 1 to 3% by mass relative to the mass of all monomers, or the total mol of all monomers. 0.1 to 0.3 mol% of a radical polymerization initiator can be added to the reaction solution.
- Examples of the polar solvent used in the method of the present invention include water, methanol, ethanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and dimethylacetamide (DMA).
- DMSO dimethyl sulfoxide
- DMF dimethylformamide
- DMA dimethylacetamide
- water is particularly preferable from the viewpoints of polymerization reactivity and safety.
- a polar polymerization initiator is added to a polar solvent containing diallylamines, sulfur dioxide and an acid, and copolymerization is carried out by appropriately stirring at room temperature or under heating conditions. A copolymer solution of diallylamines and sulfur dioxide is obtained.
- the polymerization temperature is preferably -100 ° C to 80 ° C, more preferably 5 ° C to 50 ° C.
- the polymerization time is preferably 1 to 100 hours.
- the acid remaining in the copolymer solution of diallylamines and sulfur dioxide is removed through neutralization, removal of the salt produced by the neutralization by centrifugation, or ion exchange membrane electrodialysis. It is possible.
- a copolymer of diallylamines and sulfur dioxide can be reprecipitated by adding a solvent that does not dissolve the copolymer such as alcohol or acetone, and can also be collected by filtration.
- copolymer of diallylamines and sulfur dioxide obtained by the method of the present invention is represented by the following general formula (II) or (III)
- R 1 and R 2 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X a- represents a counter ion, and a represents a valence of the counter ion). Similar structural units and the following formula (IV)
- the molecular weight of the copolymer of diallylamines and sulfur dioxide obtained by the method of the present invention is a weight average molecular weight in terms of polyethylene glycol by gel permeation chromatography (GPC), and is in the range of 2,800 to 200,000. Preferably in the range of 3,500 to 100,000, more preferably in the range of 4,000 to 80,000, still more preferably in the range of 6,000 to 60,000, Particularly preferably, it is in the range of 6,500 to 50,000.
- GPC gel permeation chromatography
- the copolymerization ratio of diallylamine units to sulfur dioxide units is (0.05 to 20): 1, preferably (0.1 to 10): 1, more preferably (0.2 to 5): 1, and still more preferably (0.4 to 2.5). ): 1, particularly preferably (0.6 to 1.5): 1.
- copolymerization of diallylamine hydrochloride and sulfur dioxide in a copolymer of diallylamine hydrochloride diallyldimethylammonium chloride, diallylmethylamine hydrochloride, diallylamine hydrochloride, etc. obtained by the method of the present invention and sulfur dioxide.
- the ratio (diallylamine hydrochloride structural unit: sulfur dioxide structural unit) is preferably (0.65 to 1.2): 1, calculated from the concentration ratio of chlorine ion and sulfur ion in the copolymer. More preferably, it is (0.7 to 1.1): 1.
- (I) Weight average molecular weight of copolymer The weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC method) using Hitachi L-6000 type high performance liquid chromatograph.
- the eluent flow path pump is Hitachi L-6000
- the detector is a Shodex RI-101 differential refractive index detector
- the column is a water gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS of Shodex Asahi Pack. -620HQ (exclusion limit molecular weight 2 million) connected in series was used. Samples were prepared with an eluent to a concentration of 0.5 g / 100 ml, and 20 ⁇ l was used.
- a 0.4 mol / liter sodium chloride aqueous solution was used as an eluent.
- the column temperature was 30 ° C. and the flow rate was 1.0 ml / min.
- a calibration curve is obtained using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard substance, and the weight average molecular weight of the copolymer ( Mw) was determined.
- Examples 1 to 7 and Comparative Example 1 a method for synthesizing a copolymer of DADMAC (diallyldimethylammonium chloride) and SO 2 is shown.
- the acid used in Examples 1 to 7 is an acid whose pKa is 4.0 or less.
- Example 1 In a 300 ml separable flask equipped with a stirrer, a thermometer and a cooling tube, 199.99 g of 65 wt% DADMAC solution (corresponding to 0.80 mol of DADMAC) and 16.67 g of 35 wt% hydrochloric acid (corresponding to 0.16 mol of hydrochloric acid; total single amount 10 mol% of the total moles of the body) and stirred uniformly. Then, after cooling to 20 ° C. or less, and a uniform solution was added SO 2 51.25g (SO 2 0.80 mole equivalent).
- Example 2 Instead of 16.67 g of 35 wt% hydrochloric acid, 33.33 g of 35 wt% hydrochloric acid (corresponding to 0.32 mol of hydrochloric acid; 20 mol% with respect to the total mol of all monomers) was used in the same manner as in Example 1. A copolymer of DADMAC and SO 2 was obtained as an aqueous solution.
- Example 3 Instead of 16.67 g of 35 wt% hydrochloric acid, 50.00 g of 35 wt% hydrochloric acid (corresponding to 0.48 mol of hydrochloric acid; 30 mol% with respect to the total mol of all monomers) was used in the same manner as in Example 1. A copolymer of DADMAC and SO 2 was obtained as an aqueous solution.
- Example 4 Instead of 16.67 g of 35 wt% hydrochloric acid, 16.52 g of 95 wt% sulfuric acid (equivalent to 0.16 mol of sulfuric acid; 10 mol% based on the total mol of all monomers) was used in the same manner as in Example 1. A copolymer of DADMAC and SO 2 was obtained as an aqueous solution. The pKa of sulfuric acid is ⁇ 3.0 (Kolthoff, Treatment on Analytical Chemistry, New York, Interscience Encyclopedia, Inc., 1959).
- Example 5 Example 1 except that 15.53 g of 99 wt% methanesulfonic acid (corresponding to 0.16 mol of methanesulfonic acid; 10 mol% based on the total mol of all monomers) was used instead of 16.67 g of 35 wt% hydrochloric acid. In the same manner as above, a copolymer of DADMAC and SO 2 was obtained as an aqueous solution. The pKa of methanesulfonic acid is ⁇ 0.6 (Brownstein, S .; Stillman, A.E.J.P.C. 1959, 63, 2061).
- Example 6 The same as Example 1 except that instead of 16.67 g of 35 wt% hydrochloric acid, 16.18 g of 97 wt% amidosulfuric acid (corresponding to 0.16 mol of amidosulfuric acid; 10 mol% with respect to the total mol of all monomers) was used. Thus, a copolymer of DADMAC and SO 2 was obtained as an aqueous solution. The pKa of amidosulfuric acid is 0.99 (Chemical Handbook Basic Edition Rev. 5 Maruzen).
- Example 7 Similar to Example 1 except that 15.21 g of 70 wt% glycolic acid (corresponding to 0.16 mol of glycolic acid; 10 mol% based on the total mol of all monomers) was used instead of 16.67 g of 35 wt% hydrochloric acid. Thus, a copolymer of DADMAC and SO 2 was obtained as an aqueous solution.
- the pKa of glycolic acid is 3.65 (Chemical Handbook Basic Edition, Rev. 5 Maruzen Co., Ltd.)
- Example 1 A copolymer of DADMAC and SO 2 was obtained as an aqueous solution in the same manner as in Example 1 except that 16.67 g of water was used instead of 16.67 g of 35 wt% hydrochloric acid.
- FIG. 1 shows the IR spectrum of the copolymer of DADMAC and SO 2 obtained in Example 1
- FIG. 2 shows the GPC chart.
- a part of the obtained solution was reprecipitated with acetone, the obtained white solid was filtered off, and dried in a vacuum at 50 ° C. for 48 hours to obtain a white powder copolymer.
- the IR spectrum of was measured.
- -SO 2 near 1,120 cm -1 and 1300 cm -1 from 1 - since due to the absorption is observed, the resulting copolymer is supported to be a copolymer of DADMAC and SO 2.
- Table 1 shows the production conditions, weight average molecular weight, polymerization yield, and copolymerization ratio of the copolymers of DADMAC and SO 2 obtained in Examples 1 to 7 and Comparative Example 1.
- the DADMAC solution pH after acid mixing is the pH of the DADMAC solution after mixing the DADMAC solution and the acid and before introducing SO 2.
- Comparative Example 1 the DADMAC solution in which no acid is mixed Of pH. As shown in Table 1, it was confirmed that when the DADMAC solution and the acid were mixed, the molecular weight of the resulting copolymer of DADMAC and SO 2 was increased as compared with the case where the DADMAC solution was not mixed with the acid. .
- the molecular weight of the copolymer obtained can be controlled by selecting the amount and type of acid. Further, the resulting copolymer, the molar ratio of DADMAC and SO 2 1: It was confirmed is close to 1 copolymer.
- Examples 8 to 9 and Comparative Example 2 a synthesis method of a copolymer of DAEMAES (diallylethylmethylammonium ethyl sulfate) and SO 2 is shown.
- the acid used in Examples 8 and 9 is an acid having a pKa of 4.0 or less.
- Example 8 In a 300 ml separable flask equipped with a stirrer, a thermometer and a cooling tube, 191.42 g of a 69.32 wt% DAEMAES solution (corresponding to DAEMAES 0.50 mol equivalent; synthesized according to the method of JP 2006-45363 A) and 35 wt% hydrochloric acid 10 .42 g (corresponding to 0.10 mol of hydrochloric acid; 10 mol% based on the total mol of all monomers) was charged and stirred uniformly. Then, after cooling to 20 ° C. or less, and a uniform solution was added SO 2 32.03g (SO 2 0.50 mole equivalent).
- Example 9 Instead of 10.42 g of 35 wt% hydrochloric acid, 10.33 g of 95 wt% sulfuric acid (equivalent to 0.10 mol of sulfuric acid; 10 mol% based on the total mol of all monomers) was used in the same manner as in Example 1. A copolymer of DAEMAES and SO 2 was obtained as an aqueous solution.
- Table 2 shows the production conditions, weight average molecular weight, polymerization yield and copolymerization ratio of the DAEMAES / SO 2 copolymers obtained in Examples 8 to 9 and Comparative Example 2.
- the acid-mixed DAEMAES solution pH is the pH of the DAEMAES solution after the DAEMAES solution and the acid are mixed and before the introduction of SO 2.
- Comparative Example 2 the DAEMAES solution with no acid mixed therein Of pH. As shown in Table 2, it was confirmed that when the DAEMAES solution and the acid were mixed, the molecular weight of the resulting DAEMAES and SO 2 copolymer was increased as compared with the case where the DAEMAES solution and the acid were not mixed. .
- Example 10 a method for synthesizing a copolymer of DAMA-HCl (diallylmethylamine hydrochloride) and SO 2 is shown.
- the acid used in Example 10 is an acid having a pKa of 4.0 or less.
- Example 10 In a 300 ml separable flask equipped with a stirrer, a thermometer and a condenser, 173.32 g of 68.15 wt% DAMA-HCl solution (corresponding to 0.80 mol of DAMA-HCl) and 16.67 g of 35 wt% hydrochloric acid (0.16 mol of hydrochloric acid) Equivalent amount: 10 mol% with respect to the total moles of all monomers) and 41.04 g of diluted water were charged and stirred uniformly. Then, after cooling to 20 ° C. or less, and a uniform solution was added SO 2 51.25g (SO 2 0.80 mole equivalent).
- Table 3 shows the production conditions, weight average molecular weight, polymerization yield, and copolymerization ratio of the copolymer of DAMA-HCl and SO 2 obtained in Example 10 and Comparative Example 3.
- the pH of the DAMA-HCl solution after mixing the acid is the pH of the DAMA-HCl solution after mixing the DAMA-HCl solution and the acid and before introducing SO 2. It means the pH of unmixed DAMA-HCl solution.
- Table 3 when the DAMA-HCl solution and the acid are mixed, the molecular weight of the resulting copolymer of DAMA-HCl and SO 2 is increased as compared with the case where the DAMA-HCl solution and the acid are not mixed. Was confirmed.
- Example 11 a method for synthesizing a copolymer of DAA-HCl (diallylamine hydrochloride) and SO 2 is shown.
- the acid used in Example 11 is an acid having a pKa of 4.0 or less.
- Example 11 In a 300 ml separable flask equipped with a stirrer, thermometer and condenser, 130.10 g of 66.76 wt% DAA-HCl solution (corresponding to 0.65 mol of DAA-HCl) and 13.55 g of 35 wt% hydrochloric acid (0.13 mol of hydrochloric acid) Equivalent amount: 10 mol% with respect to the total moles of all monomers) and 28.87 g of diluted water were charged and stirred uniformly. Then, after cooling to 20 ° C. or less, and a uniform solution was added SO 2 41.64g (SO 2 0.65 mole equivalent).
- Table 4 shows the production conditions, weight average molecular weight, polymerization yield and copolymerization ratio of the DAA-HCl / SO 2 copolymer obtained in Example 11 and Comparative Example 4.
- the DAA-HCl solution pH after the acid mixing is the pH of the DAA-HCl solution after the DAA-HCl solution and the acid are mixed and before the introduction of SO 2. It means the pH of unmixed DAA-HCl solution.
- the molecular weight of the resulting DAA-HCl / SO 2 copolymer is increased as compared with the case where the DAA-HCl solution and the acid are not mixed. Was confirmed.
- a copolymer of high-molecular-weight and water-soluble diallylamines and sulfur dioxide can be obtained. Since the metal affinity and viscosity of the copolymer are increased by increasing the molecular weight, the copolymer obtained in the present invention is expected to be used as an ink fixing agent. In recent years, high molecular weight acidic inhibitors have been demanded for various applications, and the copolymer obtained in the present invention can meet this demand.
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Abstract
Description
[1].酸及びラジカル重合開始剤の存在下、極性溶媒中で、下記一般式(I)
[2].極性溶媒中でジアリルアミン類(I)と酸とを混合し、次いで、得られたジアリルアミン類(I)の酸性溶液を二酸化硫黄と混合し、得られた混合液中において、ラジカル重合開始剤の存在下で、ジアリルアミン類(I)と二酸化硫黄とを共重合させることを特徴とする[1]に記載の方法。
[3].前記酸が、pKa4.0以下の酸である[1]又は[2]に記載の方法。
[4].前記ジアリルアミン類(I)が、ジアリルジメチルアンモニウムクロライド、ジアリルエチルメチルアンモニウムエチルサルフェイト、ジアリルメチルアミン塩酸塩及びジアリルアミン塩酸塩からなる群から選ばれるジアリルアミン類である[1]から[3]のいずれかに記載の方法。
[5].製造されたジアリルアミン類(I)と二酸化硫黄との共重合体の分子量が2,800~200,000である[1]から[4]のいずれかに記載の方法。
ジアリルジアルキルアンモニウム塩としては、例えば、ジアリルジメチルアンモニウムクロライド、ジアリルジメチルアンモニウムブロミド、ジアリルジメチルアンモニウムヨージド、ジアリルジメチルアンモニウムメチルサルフェート、ジアリルジメチルアンモニウムエチルサルフェート、ジアリルエチルメチルアンモニウムクロライド、ジアリルエチルメチルアンモニウムブロミド、ジアリルエチルメチルアンモニウムヨージド、ジアリルエチルメチルアンモニウムメチルサルフェート、ジアリルエチルメチルアンモニウムエチルサルフェート、ジアリルジエチルアンモニウムクロライド、ジアリルジエチルアンモニウムブロミド、ジアリルジエチルアンモニウムヨージド、ジアリルジエチルアンモニウムメチルサルフェート、ジアリルジエチルアンモニウムエチルサルフェート、ジアリルメチルプロピルアンモニウムクロライド、ジアリルメチルプロピルアンモニウムブロミド、ジアリルメチルプロピルアンモニウムヨージド、ジアリルメチルプロピルアンモニウムメチルサルフェート、ジアリルメチルプロピルアンモニウムエチルサルフェートを挙げることができる。
ジアリルアルキルアミン塩としては、例えば、ジアリルメチルアミン塩酸塩、ジアリルメチルアミン臭化水素酸塩、ジアリルメチルアミンヨウ化水素酸塩、ジアリルメチルアミン硫酸塩、ジアリルメチルアミンメタンスルホン酸塩、ジアリルエチルアミン塩酸塩、ジアリルエチルアミン臭化水素酸塩、ジアリルエチルアミンヨウ化水素酸塩、ジアリルエチルアミン硫酸塩、ジアリルエチルアミンメタンスルホン酸塩、ジアリルプロピルアミン塩酸塩、ジアリルプロピルアミン臭化水素酸塩、ジアリルプロピルアミンヨウ化水素酸塩、ジアリルプロピルアミン硫酸塩、ジアリルプロピルアミンメタンスルホン酸塩、を挙げることができる。
ジアリルアミン塩としては、ジアリルアミン塩酸塩、ジアリルアミン臭化水素酸塩、ジアリルアミンヨウ化水素酸塩、ジアリルアミン硫酸塩、ジアリルアミンメタンスルホン酸塩を挙げることができる。
これらの中でも、ジアリルジメチルアンモニウムクロライド(以下、本明細書において、DADMACと記載することもある)、ジアリルエチルメチルアンモニウムエチルサルフェート(以下、本明細書において、DAEMAESと記載することもある)、ジアリルメチルアミン塩酸塩(以下、本明細書において、DAMA−HClと記載することもある)又はジアリルアミン塩酸塩(以下、本明細書において、DAA−HClと記載することもある)が、その用途が広く、製造も容易なため好ましい。
なお、これら1種を単独で用いても、2種以上を組み合わせて用いてもよい。
本発明の方法において用いる酸のpKa値として、化学便覧基礎編改訂5版(丸善株式会社)に記載のpKa値を用いることができる。化学便覧基礎編改訂5版に溶媒又は液温に応じて複数の数値が記載されている場合には、酸のpKa値は、25℃の水中でのpKa値を意味するものとする。溶媒や液温に加えて、イオン強度よっても異なる数値が記載されている場合には、酸のpKa値は、イオン強度が0.1mol/lである水溶液の25℃でのpKa値を意味するものとする。
また、化学便覧基礎編改訂5版にpKa値が記載されない場合には、酸のpKa値は、25℃において窒素置換された超純水を使用してイオン強度を0.1mol/lに調整した水溶液を用意し、この水溶液のpKa値を電位差滴定装置、例えば、京都電子工業株式会社製 AT−510、により測定することで決定することができる。
なお、多価の酸の場合には、本発明の方法において用いる酸のpKaは、1段階目の解離反応におけるpKa(pKa1)を意味するものとする。
特に、本発明の方法によって得られるジアリルアミン類塩酸塩(ジアリルジメチルアンモニウムクロライド、ジアリルメチルアミン塩酸塩、ジアリルアミン塩酸塩等)と二酸化硫黄との共重合体におけるジアリルアミン類塩酸塩と二酸化硫黄との共重合比(ジアリルアミン類塩酸塩構成単位:二酸化硫黄構成単位)は、共重合体中の塩素イオンと硫黄イオンとの濃度比から算出して、好ましくは(0.65~1.2):1であり、より好ましくは(0.7~1.1):1である。
共重合体の重量平均分子量(Mw)は、日立L−6000型高速液体クロマトグラフを使用し、ゲル・パーミエーション・クロマトグラフィー(GPC法)によって測定した。溶離液流路ポンプは日立L−6000、検出器はショーデックスRI−101示差屈折率検出器、カラムはショーデックスアサヒパックの水系ゲル濾過タイプのGS−220HQ(排除限界分子量3,000)とGS−620HQ(排除限界分子量200万)とを直列に接続したものを用いた。サンプルは溶離液で0.5g/100mlの濃度に調製し、20μlを用いた。溶離液には、0.4モル/リットルの塩化ナトリウム水溶液を使用した。カラム温度は30℃で、流速は1.0ml/分で実施した。標準物質として、分子量106、194、440、600、1470、4100、7100、10300、12600、23000などのポリエチレングリコールを用いて較正曲線を求め、その較正曲線を基に共重合体の重量平均分子量(Mw)を求めた。
GPC法により得られたピーク面積比により求めた。
DADMACとSO2との共重合体溶液をメタノールにて再沈精製し、得られた再沈物をガラスフィルターにて濾過し、次いで、減圧乾燥機にて1時間乾燥させて、白色結晶を得た。得られた結晶を水に溶かして1%溶液とし、燃焼型前処理装置付イオンクロマトグラフィーにより塩素イオン濃度及び硫黄イオン濃度の測定を行った。測定された塩素イオン濃度と硫黄イオン濃度との比より共重合比を求めた。
室温条件下(23±5℃)でpHメーター(HORIBA社製)により測定した。
なお、実施例1から7で用いた酸は、そのpKaが4.0以下の酸である。
攪拌機、温度計及び冷却管を備えた300mlセパラブルフラスコ中に65wt%DADMAC溶液198.99g(DADMAC0.80モル相当分)及び35wt%塩酸16.67g(塩酸0.16モル相当分;全単量体の合計モルに対して10mol%)を仕込み、均一攪拌させた。
次いで、20℃以下に冷却した後、SO251.25g(SO20.80モル相当分)を添加して均一溶液とした。
次いで、28.5%APS(過硫酸アンモニウム)水溶液7.60g(全単量体の合計質量対して1.2wt%相当分APS)を加えて共重合させ、DADMACとSO2との共重合体を水溶液として得た。
なお塩酸のpKaは、−3.7(化学便覧基礎編 改訂5版 丸善株式会社)である。
35wt%塩酸16.67gに代えて、35wt%塩酸33.33g(塩酸0.32モル相当分;全単量体の合計モルに対して20mol%)を用いた以外は実施例1と同様にして、DADMACとSO2との共重合体を水溶液として得た。
35wt%塩酸16.67gに代えて、35wt%塩酸50.00g(塩酸0.48モル相当分;全単量体の合計モルに対して30mol%)を用いた以外は実施例1と同様にして、DADMACとSO2との共重合体を水溶液として得た。
35wt%塩酸16.67gに代えて、95wt%硫酸16.52g(硫酸0.16モル相当分;全単量体の合計モルに対して10mol%)を用いた以外は実施例1と同様にして、DADMACとSO2との共重合体を水溶液として得た。
なお硫酸のpKaは、−3.0(Kolthoff,Treatise on Analytical Chemistry,New York,Interscience Encyclopedia,Inc.,1959)である。
35wt%塩酸16.67gに代えて、99wt%メタンスルホン酸15.53g(メタンスルホン酸0.16モル相当分;全単量体の合計モルに対して10mol%)を用いた以外は実施例1と同様にして、DADMACとSO2との共重合体を水溶液として得た。
なおメタンスルホン酸のpKaは、−0.6(Brownstein,S.;Stillman,A.E.J.P.C.1959,63,2061)である。
35wt%塩酸16.67gに代えて、97wt%アミド硫酸16.18g(アミド硫酸0.16モル相当分;全単量体の合計モルに対して10mol%)を用いた以外は実施例1と同様にして、DADMACとSO2との共重合体を水溶液として得た。
なおアミド硫酸のpKaは、0.99(化学便覧基礎編 改訂5版 丸善株式会社)である。
35wt%塩酸16.67gに代えて、70wt%グリコール酸15.21g(グリコール酸0.16モル相当分;全単量体の合計モルに対して10mol%)を用いた以外は実施例1と同様にして、DADMACとSO2との共重合体を水溶液として得た。
なおグリコール酸のpKaは、3.65(化学便覧基礎編 改訂5版 丸善株式会社)である。
35wt%塩酸16.67gに代えて、水16.67gを用いた以外は実施例1と同様にして、DADMACとSO2との共重合体を水溶液として得た。
図1より1120cm−1と1300cm−1付近に−SO2−に起因する吸収が見られることから、得られた共重合体がDADMACとSO2との共重合体であることを支持する。
表1に示されるように、DADMAC溶液と酸とを混合させることによって、酸と混合させない場合と比較して、得られるDADMACとSO2との共重合体の分子量が上昇することが確認された。また、酸の量及び種類を選択することによって、得られる共重合体の分子量を制御可能なことが確認された。
また、得られた共重合体は、DADMACとSO2とのモル比1:1の共重合体に近いものであることが確認された。
なお、実施例8及び9で用いた酸は、そのpKaが4.0以下の酸である。
攪拌機、温度計及び冷却管を備えた300mlセパラブルフラスコ中に69.32wt%DAEMAES溶液191.42g(DAEMAES0.50モル相当分;特開2006−45363号公報の方法に従い合成)及び35wt%塩酸10.42g(塩酸0.10モル相当分;全単量体の合計モルに対して10mol%)を仕込み、均一攪拌させた。
次いで、20℃以下に冷却した後、SO232.03g(SO20.50モル相当分)を添加して均一溶液とした。
次いで、28.5%APS水溶液7.60g(全単量体の合計モルに対して1.2wt%相当分APS)を加えて共重合させ、DAEMAESとSO2との共重合体を水溶液として得た。
35wt%塩酸10.42gに代えて、95wt%硫酸10.33g(硫酸0.10モル相当分;全単量体の合計モルに対して10mol%)を用いた以外は実施例1と同様にして、DAEMAESとSO2との共重合体を水溶液として得た。
35wt%塩酸10.42gに代えて、水10.42gを用いた以外は実施例8と同様にして、DAEMAESとSO2との共重合体を水溶液として得た。
表2に示されるように、DAEMAES溶液と酸とを混合させることによって、酸と混合させない場合と比較して、得られるDAEMAESとSO2との共重合体の分子量が上昇することが確認された。
なお、実施例10で用いた酸は、そのpKaが4.0以下の酸である。
攪拌機、温度計及び冷却管を備えた300mlセパラブルフラスコ中に68.15wt%DAMA−HCl溶液173.32g(DAMA−HCl0.80モル相当分)及び35wt%塩酸16.67g(塩酸0.16モル相当分;全単量体の合計モルに対して10mol%)、及び希釈水41.04gを仕込み、均一攪拌させた。
次いで、20℃以下に冷却した後、SO251.25g(SO20.80モル相当分)を添加して均一溶液とした。
次いで、28.5%APS水溶液1.92g(全単量体の合計モルに対して0.15mol%相当分APS)を加えて共重合させ、DAMA−HClとSO2との共重合体を水溶液として得た。
35wt%塩酸16.67gに代えて、水16.67gを用いた以外は実施例10と同様にして、DAMA−HClとSO2との共重合体を水溶液として得た。
表3に示されるように、DAMA−HCl溶液と酸とを混合させることによって、酸と混合させない場合と比較して、得られるDAMA−HClとSO2との共重合体の分子量が上昇することが確認された。
なお、実施例11で用いた酸は、そのpKaが4.0以下の酸である。
攪拌機、温度計及び冷却管を備えた300mlセパラブルフラスコ中に66.76wt%DAA−HCl溶液130.10g(DAA−HCl0.65モル相当分)及び35wt%塩酸13.55g(塩酸0.13モル相当分;全単量体の合計モルに対して10mol%)、及び希釈水28.87gを仕込み、均一攪拌させた。
次いで、20℃以下に冷却した後、SO241.64g(SO20.65モル相当分)を添加して均一溶液とした。
次いで、28.5%APS水溶液2.08g(全単量体の合計モルに対して0.2mol%相当分APS)を加えて共重合させ、DAA−HClとSO2との共重合体を水溶液として得た。
35wt%塩酸13.55gに代えて、水13.55gを用いた以外は実施例11と同様にして、DAA−HClとSO2との共重合体を水溶液として得た。
表4に示されるように、DAA−HCl溶液と酸とを混合させることによって、酸と混合させない場合と比較して、得られるDAA−HClとSO2との共重合体の分子量が上昇することが確認された。
Claims (5)
- 極性溶媒中でジアリルアミン類(I)と酸とを混合し、次いで、得られたジアリルアミン類(I)の酸性溶液を二酸化硫黄と混合し、得られた混合液中において、ラジカル重合開始剤の存在下で、ジアリルアミン類(I)と二酸化硫黄とを共重合させることを特徴とする請求項1に記載の方法。
- 前記酸が、pKa4.0以下の酸である請求項1又は2に記載の方法。
- 前記ジアリルアミン類(I)が、ジアリルジメチルアンモニウムクロライド、ジアリルエチルメチルアンモニウムエチルサルフェイト、ジアリルメチルアミン塩酸塩及びジアリルアミン塩酸塩からなる群から選ばれるジアリルアミン類である請求項1から3のいずれかに記載の方法。
- 製造されたジアリルアミン類(I)と二酸化硫黄との共重合体の分子量が2,800~200,000である請求項1から4のいずれかに記載の方法。
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Also Published As
Publication number | Publication date |
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CN102892811A (zh) | 2013-01-23 |
EP2578618A1 (en) | 2013-04-10 |
EP2578618A4 (en) | 2016-09-07 |
EP2578618B1 (en) | 2019-01-30 |
KR20130108981A (ko) | 2013-10-07 |
JPWO2011148862A1 (ja) | 2013-07-25 |
US20130172523A1 (en) | 2013-07-04 |
KR101726018B1 (ko) | 2017-04-11 |
CN102892811B (zh) | 2015-04-01 |
US9006383B2 (en) | 2015-04-14 |
JP5748070B2 (ja) | 2015-07-15 |
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