WO2015186649A1 - ポリビニルホスホン酸ジメチル及びポリビニルホスホン酸の製造方法 - Google Patents
ポリビニルホスホン酸ジメチル及びポリビニルホスホン酸の製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Definitions
- the present invention relates to a method for producing dimethyl polyvinyl phosphonate and a method for producing polyvinyl phosphonic acid by hydrolyzing dimethyl polyvinyl phosphonate obtained by the method.
- Polyvinylphosphonates such as dimethylpolyvinylphosphonate and polyvinylphosphonic acid are being developed as polymer electrolyte materials for fuel cells, halogen-free flame retardants, metal surface treatment agents, biocompatible materials, food packaging materials, etc. Analysis of the structure and investigation of polymerization methods are actively conducted.
- Polyvinylphosphonic acid can be obtained, for example, by radical polymerization of vinylphosphonic acid.
- Polyvinylphosphonic acid obtained by radical polymerization of vinylphosphonic acid can be obtained from head-to-head or tail-to-head. It has been reported that the proportion of tail-to-tail bonding is high and the positional regularity is low (Non-patent Document 1).
- polyvinylphosphonic acid can be obtained by hydrolyzing polyvinylphosphonic acid diester obtained by radical polymerization of vinylphosphonic acid diester in the presence of an acid.
- Polyvinylphosphonic acid obtained by this hydrolysis has many head-to-tail bonds, and has higher regioregularity than that obtained by radical polymerization of vinylphosphonic acid (same as above). .
- Non-patent Document 2 Anionic polymerization is used as a method for obtaining a polyvinyl phosphonic acid diester having a higher molecular weight.
- this anionic polymerization not only a polyvinyl phosphonic acid diester having a higher molecular weight is obtained, but also the stereoregularity of polyvinyl phosphonic acid obtained by hydrolyzing the obtained polyvinyl phosphonic acid diester hydrolyzed the radical polymerized product. It is reported that the thermal behavior and solubility in solvents are different (same as above).
- Non-patent Document 3 a group transfer polymerization method (GTP) using a tricyclopentadienyl lanthanoid complex as an initiator has been reported (Non-patent Document 3).
- This GTP is a kind of living anionic polymerization, the molecular weight can be controlled by the ratio of the monomer and the initiator, and a higher molecular weight and low dispersion polymer can be obtained.
- dimethyl ester diethyl ester, diisopropyl ester, and the like are used as the vinyl phosphonic acid diester which is a raw material monomer for producing the polyvinyl phosphonic acid diester.
- dimethyl ester has high solubility in water and is suitable for hydrolysis in an aqueous solution. It is also advantageous in that it is easily available industrially.
- the solubility of the produced polymer is low, so the polymerization yield does not increase, and the molecular weight can be increased or the molecular weight can be controlled. It was not possible (cited references 2 and 3). For this reason, the molecular weight (weight average molecular weight; Mw) of the polymer produced using dimethyl vinylphosphonate as a monomer is 50,000 or less, and polyvinyl dimethyl phosphonate having a high molecular weight of 60,000 or more is obtained. The use was limited. As a result, only a low molecular weight polyvinyl phosphonic acid obtained by hydrolyzing dimethyl polyvinyl phosphonate was obtained.
- polyvinyl phosphonate diisopropyl produced using diisopropyl vinyl phosphonate as a monomer has low water solubility, and in order to produce polyvinyl phosphonic acid from this, an ester group is formed by reacting trimethylsilyl bromide in dichloromethane. After conversion to trimethylsilyl ester, it was necessary to hydrolyze in the presence of an acid, and it was difficult to hydrolyze directly in an aqueous solution (Non-patent Document 3).
- the present invention has been made in view of the above circumstances, and one of the problems is to provide a method for easily producing dimethyl polyvinylphosphonate having a high molecular weight of 60,000 or more. is there.
- Another object of the present invention is to provide a method for producing dimethylpolyvinylphosphonate containing the above high molecular weight while controlling its molecular weight.
- Another object of the present invention is to provide a method for producing polyvinyl phosphonic acid, which directly hydrolyzes dimethyl polyvinyl phosphonate including a polymer having a high molecular weight and whose molecular weight is controlled.
- dimethylpolyvinylphosphonate having a molecular weight of 60,000 or more by using a specific solvent as a polymerization solvent. It has been found that the molecular weight can be easily controlled by controlling the content of specific impurities and the like.
- polyvinyl phosphonic acid having a high molecular weight and a controlled molecular weight can be easily obtained by subjecting dimethyl polyvinyl phosphonate thus obtained to hydrolysis in the presence of an acid.
- the present invention is based on the above knowledge, and the first invention of the present invention is that polyvinyl dimethyl phosphonate is obtained by anionic polymerization from a monomer component containing dimethyl vinyl phosphonate as a main component in the presence of an anionic polymerization initiator. And a method for producing dimethyl polyvinylphosphonate, characterized in that an aliphatic ether is used as a polymerization solvent.
- the second invention of the present invention provides the above-mentioned method for producing dimethyl polyvinylphosphonate using a monomer component having an adjusted content of dimethyl phosphite.
- the third invention of the present invention provides a method for producing polyvinylphosphonic acid, wherein dimethylpolyvinylphosphonate obtained by the method of the first invention or the second invention is hydrolyzed in the presence of an acid. To do.
- the amount of dimethyl phosphite contained in the monomer component is 0.01-5 mass%.
- % Is a method for controlling the molecular weight of the resulting dimethyl polyvinylphosphonate.
- dimethyl polyvinyl phosphonate having a weight average molecular weight of 60,000 or more which has been difficult in the past, can be easily produced.
- dimethyl polyvinylphosphonate having a weight average molecular weight (Mw) controlled in the range of, for example, 10,000 to 300,000.
- polyvinyl phosphonic acid having a high molecular weight and a controlled molecular weight can be obtained by directly hydrolyzing dimethyl polyvinyl phosphonate having a high molecular weight and a controlled molecular weight.
- the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) are measured by gel permeation chromatography (GPC). Specifically, it means a value measured by the method described in the examples.
- the method for producing dimethyl polyvinyl phosphonate according to the present invention comprises, in the presence of an anionic polymerization initiator, a monomer component containing dimethyl vinyl phosphonate as a main component by anionic polymerization.
- the raw material compound for producing dimethyl polyvinylphosphonate is a monomer component containing dimethyl vinylphosphonate as a main component.
- the monomer component means a component containing substantially non-polymerizable components such as impurities derived from raw materials such as dimethyl phosphite and a residual solvent in addition to substantially only dimethyl vinylphosphonate.
- this monomer component commercially available products such as those manufactured by Katayama Chemical Co., Ltd. are commercially available, or acetylene is added to dimethyl phosphite using a known method such as a palladium complex or nickel complex as a catalyst. (For example, JP 2000-256381, JP 2001-518905, JP 2002-179691, JP 2004-075688, WO 2009/051025) and the like.
- aliphatic ethers used as a polymerization solvent include, for example, diethyl ether, dipropyl ether, methyl-tert-butyl ether (MTBE), ethyl-tert-butyl ether (ETBE), dibutyl ether, diisoamyl.
- aliphatic ethers having about 2 to 10 carbon atoms such as ether, hexyl methyl ether, octyl methyl ether, cyclopentyl methyl ether (CPME), and dicyclopentyl ether.
- MTBE is particularly preferable in terms of solubility of the monomer component and the polymerization initiator and polymerization reactivity.
- the amount of the solvent used in the anionic polymerization reaction is usually 100 to 2000 parts by weight, preferably 300 to 1000 parts by weight, based on 100 parts by weight of the monomer dimethyl vinylphosphonate.
- a high molecular weight dimethyl polyvinylphosphonate having a molecular weight of 60,000 or more which has been difficult in the past when an aromatic compound such as toluene or a cyclic ether such as THF, is used. It can be easily synthesized by anionic polymerization. Of course, as described later, it is also possible to obtain dimethyl polyvinylphosphonate having a molecular weight of 60,000 or less by the method of the present invention.
- anionic polymerization in the present invention is not particularly limited, there is a dropping polymerization method in which a monomer component solution containing dimethyl vinylphosphonate dissolved in the polymerization solvent is maintained at a predetermined temperature, and an initiator is added dropwise thereto. preferable. Moreover, it is preferable to carry out in high vacuum or inert gas atmosphere, such as nitrogen, argon, and helium.
- Examples of the initiator in anionic polymerization include organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium and hexyllithium; MeMgBr, EtMgBr, t-BuMgBr, t- Examples include basic organometallic compounds such as organomagnesium compounds (Grignard reagent) such as BuMgCl and PhMgBr.
- an organic magnesium compound can be particularly preferably used.
- the amount of the initiator used is usually in the range of 0.0001 to 0.1 mol, preferably 0.001 to 0.05 mol, relative to 1 mol of dimethyl vinylphosphonate.
- these basic organometallic compounds and Lewis acids can be used in combination.
- the Lewis acid include organoaluminum compounds such as tri-t-butylaluminum, triisobutylaluminum, and trioctylaluminum.
- the amount of Lewis acid used in combination is usually 1.0 to 50 mol, preferably 2.5 to 40 mol, based on 1 mol of the basic organometallic compound.
- the polymerization conditions in the anionic polymerization are not particularly limited, but the polymerization temperature is usually ⁇ 80 to 100 ° C., preferably ⁇ 20 to 60 ° C., more preferably 0 to 50 ° C.
- the polymerization time is usually 0.5 to 24 hours, preferably 1 to 12 hours, and more preferably 1.5 to 6 hours.
- the polymerization is carried out by dropping the initiator, it is preferable to drop the initiator in the range of 1 to 4 hours and ripen it in the range of 0.5 to 1 hour.
- the polymerization reaction can be stopped by adding a polymerization terminator to the reaction mixture when a polymer having a target molecular weight is formed.
- a polymerization terminator for example, a protic compound such as water, methanol, isopropanol, acetic acid, hydrochloric acid in methanol or the like can be used.
- the amount of the polymerization terminator used is not particularly limited, but in general, it is preferably used in the range of 1 to 100 mol with respect to 1 mol of the polymerization initiator used.
- the desired polyvinyl phosphonic acid diester is separated and obtained from the reaction mixture.
- the polymerized polyvinylphosphonic acid diester does not dissolve in the solvent, the polymer can be easily recovered by filtration.
- the polymer solution can be contacted with water to extract the polymer to the aqueous phase side, and the polyvinylphosphonic acid diester can be recovered as an aqueous polymer solution.
- a monomer component containing dimethyl vinylphosphonate as a main component (hereinafter sometimes abbreviated as “monomer component”) is used as a raw material.
- dimethyl phosphite By adjusting the content of dimethyl phosphite, it is possible to control the molecular weight of the resulting dimethyl polyvinylphosphonate.
- dimethyl polyvinylphosphonate In order to produce dimethyl polyvinylphosphonate while controlling the molecular weight, for example, the relationship between the content of dimethyl phosphite in the monomer component as a raw material and the molecular weight of the resulting dimethyl polyvinylphosphonate is experimentally investigated. However, the content of dimethyl phosphite in the raw material may be adjusted as appropriate. Preferably, a monomer component having a content of dimethyl phosphite adjusted in the range of 0.01 to 5% by mass is used. .
- dimethyl phosphite is generally contained in dimethyl vinylphosphonate as an impurity
- adjustment of the content of dimethyl phosphite in the monomer component can be accomplished by adding dimethyl phosphite or by distillation. It can carry out by removing by means, such as.
- the molecular weight of dimethyl polyvinylphosphonate obtained by this method increases as the amount of dimethyl phosphite contained in the monomer component decreases, as shown in the Examples below.
- chain transfer tends to occur and the molecular weight is decreased when the temperature is increased. Therefore, by controlling the dimethyl phosphite content at a predetermined polymerization temperature, the weight average molecular weight of dimethyl polyvinylphosphonate ( Mw) can be controlled in the range of approximately 10,000 to 300,000.
- the weight average molecular weight (Mw) of the dimethyl polyvinylphosphonate obtained by the method of the present invention can be arbitrarily selected from the above range according to the use, but is preferably in the range of 30,000 to 250,000. Particularly preferred is the range of 60,000 to 200,000.
- dimethyl polyvinyl phosphonate having a controlled molecular weight obtained by the above method is hydrolyzed in the presence of an acid to obtain polyvinyl phosphonic acid having a controlled molecular weight. be able to.
- dimethyl polyvinylphosphonate a polymer recovered as a solid from the polymerization solution may be used as the dimethyl polyvinylphosphonate.
- the polymer obtained by contacting the polymerization solution with water and extracting polyvinyl dimethyl phosphonate to the aqueous phase side is obtained.
- An aqueous solution may be used.
- Hydrolysis using an aqueous polymer solution obtained by water extraction is preferable because steps such as filtration and drying are unnecessary and the steps can be simplified.
- the acid used for the hydrolysis those usually used in the hydrolysis of phosphate esters can be used, and any of inorganic acids, organic acids and solid acids can be used. Inorganic acids such as hydrochloric acid and phosphoric acid are preferred, and hydrochloric acid is particularly preferred. Further, the amount of acid used is preferably equal to or more than 1 mol with respect to 1 mol of the ester group of the polyvinylphosphonic acid diester used for hydrolysis, usually in the range of 1 to 3 mol, preferably 1 to 2 mol, more preferably 1 to 1.5 mol. is there.
- the inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid are preferably used as an aqueous solution.
- the concentration of the acid is not particularly limited, but when hydrochloric acid is used as the acid, the amount of acid used can be reduced by lowering the ratio of water as the solvent, so concentrated hydrochloric acid (12 mol / L) is used. It is preferable.
- Hydrolysis is usually performed in a solvent composed of water, a hydrophilic solvent, or a mixed solvent thereof.
- the hydrophilic solvent include polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether,
- glycol ether solvents such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether.
- the amount of the solvent used is usually in the range of 100 to 1000 parts by weight, preferably 400 to 600 parts by weight, more preferably 300 to 500 parts by weight with respect to 100 parts by weight of the polyvinylphosphonic diester used for hydrolysis.
- an antifoaming agent may be used as long as the reaction is not inhibited.
- the antifoaming agent generally known antifoaming agents having a foam breaking effect or a foam suppressing effect can be used.
- oil-type silicone antifoaming agents, emulsion-type silicone antifoaming agents, foam-breaking polymer-type antifoaming agents such as nonionic polyethers, special nonionic surfactants, and polyether-modified methylalkylpolysiloxane Examples thereof include a polymer, a polyethylene glycol type nonionic surfactant, and a vegetable oil-based antifoaming agent. These may be used alone or in combination of two or more.
- the amount of the antifoaming agent used is usually in the range of 0.001 to 1 part by weight, preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the solvent.
- the reaction temperature in the hydrolysis is not particularly limited, but is usually selected from the range of 80 to 100 ° C., preferably 90 to 100 ° C., more preferably 95 to 100 ° C. of water.
- the reaction time may be appropriately selected in consideration of the reaction temperature, and is usually in the range of 2 to 24 hours, preferably 4 to 16 hours, more preferably 6 to 8 hours.
- the hydrolysis reaction is preferably performed while removing methanol generated by the hydrolysis.
- the weight average molecular weight (Mw) of the polyvinylphosphonic acid obtained by the above hydrolysis is in the range of 10,000 to 300,000, preferably 30,000 to 250,000, particularly preferably 60,000 to 200,000. is there.
- the molecular weight of polyvinylphosphonic acid obtained by hydrolysis is theoretically lower than that of the polymer before hydrolysis due to elimination of the protecting group.
- the weight average molecular weight (Mw) measured by GPC according to the method described in the examples is measured as a polymer having a higher molecular weight than that before hydrolysis due to the interaction with the column. Is done. Therefore, in consideration of this point, it is preferable to adjust the anionic polymerization conditions so that the molecular weight of the polymer after hydrolysis falls within a desired range.
- the polymer solution after hydrolysis contains an excessive amount of acid, it is preferable to remove the acid.
- the polymer solution obtained by hydrolysis may be treated as it is or after being diluted to an appropriate concentration with water.
- the acid removal treatment method may be any method as long as the acid can be separated and removed from the polymer solution. Specific examples include reprecipitation using a poor solvent of polyvinylphosphonic acid, adsorption treatment, ultrafiltration, dialysis, electrodialysis, ion exchange membrane, and the like, one or more of these. It is desirable to carry out in combination.
- Polyvinylphosphonic acid after the above acid removal treatment can be used as a polymer solution as it is, but it should be used after further concentration, reprecipitation, solvent replacement, solvent extraction, drying, etc. as necessary. You can also.
- the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymers obtained in the examples were measured by gel permeation chromatography (GPC), and calculated from converted values using standard polyethylene oxide samples.
- GPC measuring device LC-Solution manufactured by SHIMADZU Column: Shodex SB-805HQ, SB-804HQ Precolumn: Shodex SB-G Column temperature: 40 ° C Mobile phase: 0.2 M NaCl aqueous solution Flow rate: 0.5 mL / min Detector: RI detector
- hydrolysis rate was calculated by 1 H-NMR, based on the integrated value of the peak derived from the methoxy group of dimethyl polyvinylphosphonate.
- NMR measuring device JEOL AL-400 Solvent: heavy water
- the polymer concentration in the aqueous solution was obtained by drying 0.5 mL of the aqueous solution on a petri dish at 120 ° C. for 2 hours under reduced pressure, and then measuring the weight of the residue.
- Example 1 Production example (1) of dimethyl polyvinylphosphonate: A glass container having a capacity of 10 L was prepared, the adsorbed water in the container was removed by heating, and nitrogen substitution was further performed. In this container, 980 g of monomer component (1) (dimethyl phosphite content 0.02%) and methyl t-butyl ether (MTBE) 6444 g prepared by distillation to a dimethyl vinylphosphonate purity of 99.8% were added. The reaction system was cooled to 0 ° C.
- monomer component (1) dimethyl phosphite content 0.02%
- MTBE methyl t-butyl ether
- t-BuMgCl prepared to 0.25 mol / L with THF (0.12 mol as t-BuMgCl) was added dropwise over 1 hour while maintaining the temperature in the system at 0 ° C., and the polymerization reaction was allowed to proceed. After the entire amount of t-BuMgCl was dropped, the mixture was aged for 30 minutes to complete the conversion of dimethyl vinylphosphonate.
- Example 2 Production examples (2) to (4) of dimethyl polyvinylphosphonate: Dimethyl phosphite was added to the monomer component (1) used in Example 1, and the monomer component (2) having a purity of 99.1% (dimethyl phosphite content 0.7%), Monomer component (3) with a purity of 98.5% (dimethyl phosphite content 1.3%) and monomer component (4) with a purity of 98.3% (dimethyl phosphite content 1.5%) ) Were prepared respectively.
- Polyvinyl chloride was prepared by the same procedure as in Example 1 except that each of the monomer components (2) to (4) was used, and an initiator (t-BuMgCl) and a stopper (methanol) in the amounts shown in Table 1 below were used. Dimethyl phosphonate was obtained (Production Examples (2) to (4)).
- Example 3 Production examples (5) to (8) of dimethyl polyvinylphosphonate: Distillation of 83.5% pure dimethyl vinylphosphonate (containing 3.1% dimethyl phosphite, 13.1% toluene, 0.2% methanol, 0.1% others) to a purity of 99.7 % Monomer component (5) (dimethyl phosphite content 0.04%), purity 99.3% monomer component (6) (dimethyl phosphite content 0.32%), purity 98 9.9% monomer component (7) (dimethyl phosphite content 0.64%) and purity 98.6% monomer component (8) (dimethyl phosphite content 0.96%) Each was prepared.
- a glass container with a capacity of 500 mL was prepared, the adsorbed water in the container was removed by heating, and nitrogen substitution was further performed.
- this vessel 40.0 g of monomer component (5) and 245.7 g of methyl t-butyl ether (MTBE) were placed, and the reaction system was cooled to 0 ° C.
- MTBE methyl t-butyl ether
- dimethyl polyvinylphosphonate was obtained by the same procedure (Production Examples (6) to (8)). The yield of the obtained dimethyl polyvinylphosphonate and the GPC measurement results are shown in Table 1 below.
- Example 4 Production examples (9) to (12) of dimethyl polyvinylphosphonate: Except for carrying out the polymerization reaction at a temperature in the reaction system of 25 ° C., dimethyl polyvinylphosphonate was obtained by the same procedure as in Example 3 (Production Examples (9) to (12)). The yield of the obtained dimethyl polyvinylphosphonate and the GPC measurement results are shown in Table 1 below.
- Example 5 Production examples (13) to (16) of dimethyl polyvinylphosphonate: Except for carrying out the polymerization reaction at a temperature of 50 ° C. in the reaction system, dimethyl polyvinylphosphonate was obtained by the same procedure as in Example 3 (Production Examples (13) to (16)).
- FIG. 2 shows the relationship between the weight average molecular weight (Mw) of the dimethyl polyvinylphosphonate obtained in Examples 3 to 5 and the dimethyl phosphite concentration.
- Example 6 Production examples (17) to (20) of dimethyl polyvinylphosphonate: Dimethyl phosphite was added to the monomer component (1) used in Example 1, and the monomer component (17) having a purity of 98.9% (dimethyl phosphite content 0.9%), Monomer component (18) with a purity of 98.3% (dimethyl phosphite content 1.5%), monomer component (19) with a purity of 96.3% (dimethyl phosphite content 3.5%) ) And 95.1% pure monomer component (20) (dimethyl phosphite content 4.7%).
- dimethylpolyvinylphosphonate was obtained by the same procedure as in Example 3 except that the amounts of initiator (t-BuMgCl) and terminator (methanol) shown in Table 1 were used (production) Examples (17) to (20)).
- Table 1 shows the yield and GPC measurement results of the obtained dimethyl polyvinylphosphonate. Moreover, the relationship between the weight average molecular weight (Mw) of the dimethyl polyvinylphosphonate obtained in Example 6 and the dimethyl phosphite concentration is shown in FIG.
- Example 7 Production example (21) of dimethyl polyvinylphosphonate: A glass container with a capacity of 500 mL was prepared, the adsorbed water in the container was removed by heating, and nitrogen substitution was further performed. In this container, 40.0 g of monomer component (19) (dimethyl phosphite content 4.3%) adjusted to 95.5% dimethyl vinylphosphonate purity and 245.0 g of methyl t-butyl ether (MTBE) And the reaction system was heated to 50 ° C.
- monomer component (19) dimethyl phosphite content 4.3%) adjusted to 95.5% dimethyl vinylphosphonate purity and 245.0 g of methyl t-butyl ether (MTBE)
- Example 8 Production Examples and Hydrolysis Examples of Polyvinylphosphonic Acid (1): (1) A glass container having a capacity of 500 mL was prepared, the adsorbed water in the container was removed by heating, and nitrogen substitution was further performed. In this container, 40.0 g of the monomer component (18) having the same purity as that used in Example 6 (18) (dimethyl phosphite content 1.5%) and methyl t-butyl ether (MTBE) 245 0.0 g was added and the reaction system was cooled to 0 ° C.
- MTBE methyl t-butyl ether
- PhMgBr (7.4 mmol as PhMgBr) prepared to 0.25 mol / L with THF was added dropwise over 1 hour while maintaining the temperature in the system at 0 ° C., and the polymerization reaction was allowed to proceed. After the entire amount of PhMgBr was dropped, the mixture was aged for 30 minutes to complete the conversion of dimethyl vinylphosphonate.
- Example 9 Production examples and hydrolysis examples of polyvinylphosphonic acid (2): (1) Production of dimethyl polyvinylphosphonate A glass container having a capacity of 500 mL was prepared, and the adsorbed water in the container was removed by heating, followed by nitrogen substitution. In this vessel, 40.3 g of dimethyl vinylphosphonate and 246.2 g of methyl t-butyl ether were placed, and the reaction system was cooled to 0 ° C. After cooling, 27.0 g of t-BuMgCl prepared with THF to 0.25 mol / L (7.5 mmol as t-BuMgCl) was added dropwise over 1 hour while maintaining the temperature in the system at 0 ° C., and the polymerization reaction proceeded. I let you. After the entire amount of t-BuMgCl was dropped, the mixture was aged for 30 minutes to complete the conversion of dimethyl vinylphosphonate.
- t-BuMgCl prepared with THF to 0.25 mol / L (7.5 mmol as
- Acid removal step 283.4 g of methyl ethyl ketone was added to the reaction solution obtained in the hydrolysis step to precipitate a polyvinylphosphonic acid solid, and the solid was recovered by filtration.
- the recovered solid was dissolved in 157.9 g of ion-exchanged water, and 70.0 g of ion-exchange resin (Dowex Monosphere-550A, manufactured by Dow Chemical Co., Ltd.) was added and stirred for 2 hours.
- the polymer concentration of the aqueous solution was 12.2% by mass (22.0 g as a solid content; yield 92%).
- the residual chlorine ion was less than 1% based on the polymer.
- Comparative Example 1 Production example (22) of dimethyl polyvinylphosphonate: A comparative example in which a solvent other than aliphatic ether is used as the polymerization solvent is shown below. That is, a glass container having a capacity of 500 mL was prepared, the adsorbed water in the container was removed by heating, and nitrogen substitution was further performed. In this container, the monomer component (18) having the same purity as that used in Example 6 (18) (dimethyl phosphite content 1.5%) and 266.7 g (2.89 mol) of toluene were added. The reaction system was cooled to 0 ° C.
- PhMgBr (7.4 mmol as PhMgBr) prepared to 0.25 mol / L with THF was added dropwise over 1 hour while maintaining the temperature in the system at 0 ° C., and the polymerization reaction was allowed to proceed. After the entire amount of PhMgBr was dropped, the mixture was aged for 30 minutes to complete the conversion of dimethyl vinylphosphonate.
- dimethyl polyvinyl phosphonate having a weight average molecular weight of 60,000 or more which has been difficult in the past, can be easily produced, and the molecular weight can be controlled.
- this dimethyl polyvinylphosphonate and polyvinylphosphonic acid can be used as polymer electrolyte materials for fuel cells, halogen-free flame retardants, metal surface treatment agents, biocompatible materials, food packaging materials, etc., as polymers having different physical properties. It is a thing.
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Abstract
Description
本発明のポリビニルホスホン酸ジメチルの製造方法は、アニオン重合開始剤の存在下、ビニルホスホン酸ジメチルを主成分として含む単量体成分から、アニオン重合によりポリビニルホスホン酸ジメチルを製造する方法であって、重合溶媒として脂肪族エーテルを用いることを特徴とする。
本発明では、上記方法により得られた分子量が制御されたポリビニルホスホン酸ジメチルを、酸の存在下、加水分解することにより、分子量が制御されたポリビニルホスホン酸を得ることができる。
重合原料として用いた単量体成分のビニルホスホン酸ジメチル純度及び亜リン酸ジメチル含有量の測定は、ガスクロマトグラフィーにより行った。
ガスクロ装置:SHIMADZU社製 GC-2010
カラム:DB-1
測定条件:試料気化室250℃、検出器280℃
カラムオーブン100℃3分保持、昇温速度15℃/分で280℃
まで昇温、280℃で20分保持
実施例において得られたポリマーの重量平均分子量(Mw)及び分子量分布(Mw/Mn)は、ゲルパーミエイションクロマトグラフィー(GPC)により測定し、標準ポリエチレンオキサイド試料を用いた換算値から算出した。
GPC測定装置:SHIMADZU社製LC-Solution
カラム:Shodex SB-805HQ、SB-804HQ
プレカラム:Shodex SB-G
カラム温度:40℃
移動相:0.2M NaCl水溶液
流量:0.5mL/min
検出器:RI検出器
ポリマー中に残存する塩化物イオン濃度は、イオンクロマトグラフ法により定量した。
IC測定装置:DIONEX ICS-2000
カラム:AS17-C
溶離液:KOH
検出器:電気伝導度検出器
加水分解率の測定は1H-NMRによって、ポリビニルホスホン酸ジメチルのメトキシ基に由来するピークの積分値によって算出した。
NMR測定装置:JEOL AL-400
溶媒:重水
水溶液中のポリマー濃度は、水溶液 0.5mLをシャーレ上で120℃、2時間減圧乾燥した後、残分の重量を測定して求めた。
ポリビニルホスホン酸ジメチルの製造例(1):
容量10Lのガラス容器を準備し、加熱によって容器内の吸着水を除き、さらに窒素置換を行った。この容器内に、蒸留によりビニルホスホン酸ジメチル純度を99.8%に調製した単量体成分(1)(亜リン酸ジメチル含有量0.02%)980g及びメチルt-ブチルエーテル(MTBE)6444gを入れ、反応系内を0℃に冷却した。
ポリビニルホスホン酸ジメチルの製造例(2)~(4):
実施例1で用いた単量体成分(1)に、亜リン酸ジメチルを添加して、純度99.1%の単量体成分(2)(亜リン酸ジメチル含有量0.7%)、純度98.5%の単量体成分(3)(亜リン酸ジメチル含有量1.3%)及び純度98.3%の単量体成分(4)(亜リン酸ジメチル含有量1.5%)をそれぞれ調製した。
ポリビニルホスホン酸ジメチルの製造例(5)~(8):
純度83.5%の粗ビニルホスホン酸ジメチル(亜リン酸ジメチル3.1%、トルエン13.1%、メタノール0.2%、その他0.1%を含む)を蒸留して、純度99.7%の単量体成分(5)(亜リン酸ジメチル含有量0.04%)、純度99.3%の単量体成分(6)(亜リン酸ジメチル含有量0.32%)、純度98.9%の単量体成分(7)(亜リン酸ジメチル含有量0.64%)及び純度98.6%の単量体成分(8)(亜リン酸ジメチル含有量0.96%)をそれぞれ調製した。
ポリビニルホスホン酸ジメチルの製造例(9)~(12):
反応系内の温度を25℃として重合反応を行う以外は実施例3と同様の手順によりポリビニルホスホン酸ジメチルを得た(製造例(9)~(12))。得られたポリビニルホスホン酸ジメチルの収率及びGPC測定結果を後記表1に示す。
ポリビニルホスホン酸ジメチルの製造例(13)~(16):
反応系内の温度を50℃として重合反応を行う以外は実施例3と同様の手順によりポリビニルホスホン酸ジメチルを得た(製造例(13)~(16))。
ポリビニルホスホン酸ジメチルの製造例(17)~(20):
実施例1で用いた単量体成分(1)に、亜リン酸ジメチルを添加して、純度98.9%の単量体成分(17)(亜リン酸ジメチル含有量0.9%)、純度98.3%の単量体成分(18)(亜リン酸ジメチル含有量1.5%)、純度96.3%の単量体成分(19)(亜リン酸ジメチル含有量3.5%)及び純度95.1%の単量体成分(20)(亜リン酸ジメチル含有量4.7%)をそれぞれ調製した。
ポリビニルホスホン酸ジメチルの製造例(21):
容量500mLのガラス容器を準備し、加熱によって容器内の吸着水を除き、さらに窒素置換を行った。この容器内にビニルホスホン酸ジメチル純度を95.5%に調製した単量体成分(19)(亜リン酸ジメチル含有量4.3%)40.0g及びメチルt-ブチルエーテル(MTBE)245.0gを入れ、反応系内を50℃に加熱した。
ポリビニルホスホン酸の製造例および加水分解例(1):
(1)容量500mLのガラス容器を準備し、加熱によって容器内の吸着水を除き、さらに窒素置換を行った。この容器内に実施例6で用いたものと同じ純度98.3%の単量体成分(18)(亜リン酸ジメチル含有量1.5%)40.0g及びメチルt-ブチルエーテル(MTBE)245.0gを入れ、反応系内を0℃に冷却した。
ポリビニルホスホン酸の製造例および加水分解例(2):
(1)ポリビニルホスホン酸ジメチルの製造
容量500mLのガラス容器を準備し、加熱によって容器内の吸着水を除き、さらに窒素置換を行った。この容器内に、ビニルホスホン酸ジメチル40.3g及びメチルt-ブチルエーテル246.2gを入れ、反応系内を0℃に冷却した。冷却後、THFによって0.25mol/Lに調製したt-BuMgCl 27.0g(t-BuMgClとして7.5mmol)を系内の温度を0℃に保ちつつ1時間かけて滴下し、重合反応を進行させた。t-BuMgClを全量滴下後、30分間熟成し、ビニルホスホン酸ジメチルの転化を終了させた。
反応液にイオン交換水120.9gを加えて60分撹拌し、反応を停止させた。撹拌終了後、30分静置し有機相と水相を分液することによりポリビニルホスホン酸ジメチルの水溶液167gを回収した。
得られたポリビニルホスホン酸ジメチルは、GPC測定の結果、Mw=125,000、Mw/Mn=4.40であった。また、水溶液のポリマー濃度は24.5質量%であった(固形分として40.9g;収率102%)。
容量500mLのガラス容器に上記のポリビニルホスホン酸ジメチル水溶液124.9g(固形分として30.6g;ビニルホスホン酸ジメチル換算で0.22mol)を加え、ポリビニルホスホン酸ジメチル濃度が30%になるまで100℃で濃縮を行った。濃縮した液に12mol/L塩酸85.6g(0.84mol)を加え、100℃で6時間反応させた。反応中はディーン・スターク装置を用いて副生物として生成したメタノールを除去した。反応終了後、1H-NMRの測定によってポリビニルホスホン酸ジメチルが完全に加水分解されていることを確認した。
加水分解工程で得られた反応液にメチルエチルケトン283.4gを加え、ポリビニルホスホン酸の固体を析出させ、ろ過によって固体を回収した。回収した固体をイオン交換水157.9gに溶解させ、イオン交換樹脂(ダウエックスモノスフィア―550A、ダウ・ケミカル社製、商標)70.0gを加えて2時間撹拌した。
得られたポリビニルホスホン酸は、GPC測定の結果、Mw=170,000、Mw/Mn=3.80であった。また、水溶液のポリマー濃度は12.2質量%であった(固形分として22.0g;収率92%)。また、塩素分析の結果、残存塩素イオンはポリマーに対して1%未満であった。
ポリビニルホスホン酸ジメチルの製造例(22):
重合溶媒として、脂肪族エーテル以外の溶媒を用いた場合の比較例を以下に示す。すなわち、容量500mLのガラス容器を準備し、加熱によって容器内の吸着水を除き、さらに窒素置換を行った。この容器内に、実施例6で用いたものと同じ純度98.3%の単量体成分(18)(亜リン酸ジメチル含有量1.5%)及びトルエン266.7g(2.89mol)を入れ、反応系内を0℃に冷却した。
Claims (8)
- アニオン重合開始剤の存在下、ビニルホスホン酸ジメチルを主成分として含む単量体成分からアニオン重合によりポリビニルホスホン酸ジメチルを製造する方法であって、重合溶媒として脂肪族エーテルを用いることを特徴とするポリビニルホスホン酸ジメチルの製造方法。
- 前記脂肪族エーテルが、炭素数2~10のものである請求項1記載のポリビニルホスホン酸ジメチルの製造方法。
- 前記単量体成分として、亜リン酸ジメチルの含有量が調整された単量体成分を用いる請求項1または2記載のポリビニルホスホン酸ジメチルの製造方法。
- 前記単量体成分中の亜リン酸ジメチルの含有量を、0.01~5質量%の範囲に調整する請求項1ないし3の何れかの項記載のポリビニルホスホン酸ジメチルの製造方法。
- 請求項1~4のいずれかの項記載の方法により得られたポリビニルホスホン酸ジメチルを、酸の存在下で加水分解するポリビニルホスホン酸の製造方法。
- アニオン重合により得られた重合液を水と接触させて、ポリビニルホスホン酸ジメチルを水相側に抽出し、得られたポリマー水溶液を用いて加水分解を行う請求項5記載のポリビニルホスホン酸の製造方法。
- ビニルホスホン酸ジメチルを主成分として含む単量体成分のアニオン重合において、単量体成分に含まれる亜リン酸ジメチルの量を0.01~5質量%の範囲で調整することを特徴とする、生成ポリビニルホスホン酸ジメチルの分子量制御方法。
- 更に温度を、0℃ないし50℃の範囲内で調整する、請求項7記載の生成ポリビニルホスホン酸ジメチルの分子量の制御方法。
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