CN111757898B - Allylamine copolymer and process for producing the same - Google Patents
Allylamine copolymer and process for producing the same Download PDFInfo
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- CN111757898B CN111757898B CN201980014562.2A CN201980014562A CN111757898B CN 111757898 B CN111757898 B CN 111757898B CN 201980014562 A CN201980014562 A CN 201980014562A CN 111757898 B CN111757898 B CN 111757898B
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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
- 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
- C08F226/04—Diallylamine
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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
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- 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
Abstract
Disclosed is an allylamine copolymer having a desired composition and polymerization degree, which is obtained by polymerizing a monoallylamine monomer and an ethylenically unsaturated monomer having different polymerizability in water at a high yield. The object of the present invention is achieved by an allylamine copolymer having a constituent unit A derived from a monoallylamine-based monomer a and a constituent unit B derived from an ethylenically unsaturated monomer B, wherein the molar ratio of the constituent unit A/the constituent unit B is 0.4 to 25.
Description
Technical Field
The present invention relates to an allylamine copolymer and a method for producing the same. More particularly, the present invention relates to copolymers of monoallylamine-based monomers and ethylenically unsaturated monomers having a copolymerization composition that has not been achieved in the prior art, and a manufacturing process that can efficiently obtain such copolymers.
Background
It is considered that an allyl monomer, particularly a monoallylamine monomer is susceptible to chain transfer which is degraded by the resonance stability of an allyl radical, and is inferior in radical polymerizability. On the other hand, it is known that an ethylenically unsaturated monomer such as (meth) acrylic acid is a monomer having high radical polymerizability. Therefore, the copolymers cannot be obtained at almost equimolar ratios between the two. When 2 kinds of monomers are copolymerized in water, it is considered that only ethylenically unsaturated monomers such as (meth) acrylic acid having high radical polymerizability are polymerized due to the difference in polymerizability and polymerization rate between the two monomers in the conventional art, and almost homopolymers are formed.
As a method for copolymerizing a monoallylamine-based monomer and an ethylenically unsaturated monomer such as (meth) acrylic acid, a method of reacting an addition salt such as hydrochloride of a monoallylamine-based monomer with (meth) acrylic acid in a methanol solvent has been proposed (for example, see patent document 1).
However, in the method described in patent document 1, it is reported that the yield of monoallylamine hydrochloride/(meth) acrylic acid copolymer is 50% or less. In addition, since monoallylamine hydrochloride homopolymer and (meth) acrylic acid homopolymer are also produced simultaneously in this method, complicated operations such as filtration and removal of these are required.
Further, according to additional tests by the present inventors, the method described in patent document 1 has a problem that the solubility of the obtained copolymer in water is low. The copolymer is soluble in water only in a certain pH range, and therefore a copolymer of a desired composition cannot be obtained in practice, and there is a high possibility that a homopolymer of acrylic acid, or a mixture of homopolymers of both monomers is substantially produced.
In summary, no practical synthesis method has been found for copolymers of monoallylamine monomers and ethylenically unsaturated monomers.
Documents of the prior art
Patent literature
Patent document 1: japanese unexamined patent publication No. 2001-106736
Non-patent document
Non-patent document 1: zetian Xifu et al 4, journal of the Nippon oil chemical society, vol.46, no. 2 (1997), pp.191-203
Disclosure of Invention
Problems to be solved by the invention
As described above, although it is reported in each of the prior art documents that a monoallylamine hydrochloride/(meth) acrylic acid copolymer can be synthesized by the synthesis method described in the document, there is no evidence of obtaining a desired copolymer, and there are problems such as poor solubility in water and low yield.
In view of the above-described limitations of the prior art, an object of the present invention is to provide an allylamine copolymer having a desired composition and polymerization degree, which is obtained by polymerizing monoallylamine-based monomers and ethylenically unsaturated monomers having different polymerizability in water at a high yield, and a production method capable of producing such an allylamine copolymer at a practical efficiency and cost.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object and as a result, have found that a copolymer of a monoallylamine monomer and an ethylenically unsaturated monomer can be easily produced under normal pressure and stable heating conditions by adding an ethylenically unsaturated monomer having excellent radical polymerizability such as (meth) acrylic acid and the like which is excellent in polymerizability in a water solvent dropwise (adding while dropping) to the monoallylamine monomer, and that the copolymer is water-soluble or water-dispersible even if the ratio of acrylic acid is large, and have completed the present invention.
Namely, the present invention is:
[1] an allylamine copolymer having a constituent unit A derived from a monoallylamine-based monomer a and a constituent unit B derived from an ethylenically unsaturated monomer B, wherein the molar ratio of the constituent unit A/the constituent unit B is 0.4 to 25.
Further, the following [2] to [15] are an embodiment or a preferred embodiment of the present invention, respectively.
[2] The allylamine-based copolymer according to [1], which is water-soluble or water-dispersible at pH2, 7 and 12.
[3] The allylamine copolymer according to [1] or [2], wherein the intrinsic viscosity [ η ] is 0.03 (dl/g) or more.
[4] The allylamine copolymer according to any one of [1] to [3], wherein the monoallylamine-based monomer a contains at least 1 monomer selected from monoallylamine hydrochloride, monoallylamine sulfate, monoallylamine phosphate, and monoallylamine amide sulfate.
[5] The allylamine-based copolymer according to any one of [1] to [4], wherein the ethylenically unsaturated monomer b contains (meth) acrylic acid.
[6] The composition comprising the allylamine copolymer according to any one of [1] to [5], wherein the total content of the unreacted monoallylamine-based monomer a and the ethylenically unsaturated monomer b is 15% by weight or less.
[7] A process for producing an allylamine copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, which comprises a step of dropping an aqueous solution of the ethylenically unsaturated monomer b into an aqueous solution of the monoallylamine-based monomer a.
[8] The method according to [7], wherein the step is carried out at a temperature ranging from 0 to 100 ℃.
[9] The process according to [7] or [8], wherein the molar ratio of the monoallylamine-based monomer a to the ethylenically unsaturated monomer b supplied to the above step is 1:5 to 40:1.
[10] the process according to any one of [7] to [9], wherein the allylamine copolymer produced has a molar ratio A/B of the constituent unit A derived from the monoallylamine-based monomer a to the constituent unit B derived from the ethylenically unsaturated monomer B of 0.4 to 25.
[11] The method according to any one of [7] to [10], wherein the allyl amine copolymer has a molar ratio A/(A + B) of the constituent unit A to the total of the constituent unit A and the constituent unit B in a range of a molar ratio a/(a + B) ± 25% of the monoallylamine-based monomer a supplied to the step to the total of the monoallylamine-based monomer a and the ethylenically unsaturated monomer B supplied to the step.
[12] The process according to any one of [7] to [11], wherein the yield of the allylamine-based copolymer from the feed is 70% by weight or more.
[13] The method according to any one of [7] to [12], wherein an amount of the monoallylamine-based monomer a remaining unpolymerized after the step is 70% by weight or less of an amount of the monoallylamine-based monomer a supplied to the step.
[14] An article comprising the allylamine-based copolymer according to any one of [1] to [5], wherein the article is: a dispersant, an ink jet printing agent, an adhesive, a papermaking agent, an antistatic agent, a coating material, a wastewater treatment agent, an anchor coat agent (anchor coat agent), a synthetic resin film, a dye fixing agent, or a molding resin.
Effects of the invention
According to the present invention, there is provided a copolymer of a monoallylamine-based monomer and an ethylenically unsaturated monomer having a desired composition and degree of polymerization, which could not be produced by the prior art. The copolymer is water-soluble or water-dispersible in a wide pH range, and is suitable for use in applications requiring water-solubility or water-dispersibility, such as printing materials, adhesives, and paints.
In addition, according to the production method of the present invention, a monoallylamine-based monomer and an ethylenically unsaturated monomer can be polymerized into a copolymer in a high yield in water, and an allylamine-based copolymer having a desired composition and degree of polymerization can be produced with practical efficiency and at a low cost.
Detailed Description
Allylamine copolymer
The present invention is an allylamine copolymer having a constituent unit A derived from a monoallylamine-based monomer a and a constituent unit B derived from an ethylenically unsaturated monomer B, wherein the molar ratio of the constituent unit A/the constituent unit B is 0.4 to 25.
That is, the allylamine copolymer of the present invention may contain the constituent unit a derived from the monoallylamine-based monomer a and the constituent unit B derived from the ethylenically unsaturated monomer B at a predetermined molar ratio, and may contain or may not contain other constituent units.
The molar ratio of the constituent unit a/the constituent unit B in the allylamine copolymer of the present invention is 0.4 to 25, which means that: monoallylamine-based monomers a and ethylenically unsaturated monomers b can be polymerized in a wide range (including copolymerization at an equivalent molar ratio) at the desired copolymerization ratio, indicating that copolymers not obtainable in the prior art are obtained.
The molar ratio of the constituent unit a/the constituent unit B in the allylamine copolymer of the present invention is preferably 0.4 to 15, more preferably 0.5 to 12, and particularly preferably 0.6 to 10, because the characteristic functions of both functional groups can be more strongly exhibited.
The molar ratio of the constituent unit a/constituent unit B in the allylamine copolymer of the present invention is identified by measuring the amounts of the constituent unit a derived from a monoallylamine-based monomer a such as allylamine hydrochloride and the constituent unit B derived from an ethylenically unsaturated monomer B such as methacrylic acid, which constitute the copolymer, by elemental analysis.
The allylamine-based copolymers of the present invention are preferably water soluble or water dispersible at pH2, 7 and 12. Here, "water-soluble" means that the allylamine-based copolymer is dissolved in water to form a transparent solution, and "water-dispersibility" means that the allylamine-based copolymer is dispersed in water (including a case where the allylamine-based copolymer is partially dissolved) and undissolved solid components having a size that can be visually observed do not remain.
The above-mentioned being water-soluble or water-dispersible at pH2, 7 and 12 means: this copolymer is water-soluble or water-dispersible over a wide pH range, and indirectly indicates that an allylamine-based copolymer having a desired composition (molar ratio of constituent unit a/constituent unit B) can be obtained.
On the other hand, when a monoallylamine hydrochloride homopolymer is present in admixture with a homopolymer of an ethylenically unsaturated monomer such as a (meth) acrylic acid homopolymer, since it is insoluble in water because it forms an ionic complex or the like at any of the above pH, an allylamine-based copolymer having a desired composition cannot be obtained in high yield when it is insoluble in water at any of the above pH, and a homopolymer of an ethylenically unsaturated monomer b or other homopolymers may be formed from the remaining ethylenically unsaturated monomer b. In this case, there is a concern that complicated work such as filtration and removal of homopolymers or the like of the ethylenically unsaturated monomer b is required, and the like are not economical.
The water solubility or water dispersibility of the allylamine-based copolymer at pH2, 7 and 12 can be judged by the following method: the presence or absence of water solubility or water dispersibility is determined by dissolving an allylamine copolymer in water, adjusting the pH of the aqueous solution to 2, 7, and 12 using an aqueous NaOH solution or the like, and visually observing the formation of a precipitate.
The allylamine copolymer of the present invention is more preferably water-soluble or water-dispersible at a pH of 0 to 14, and particularly preferably water-soluble at a pH of 0 to 14.
The molecular weight of the allylamine copolymer of the present invention is not particularly limited, and a (co) polymer having an appropriate molecular weight can be suitably polymerized in consideration of the desired physical properties and use. In the case where the allylamine-based copolymer is soluble in an eluent, the molecular weight of the allylamine-based copolymer can be measured by GPC. In addition, the intrinsic viscosity [ η ] can be indirectly evaluated by measurement.
The intrinsic viscosity [ η ] is preferably 0.03dl/g or more from the viewpoint of having a viscosity suitable for the use in a dispersant, a binder, a coating material, or the like and enabling polymerization with practically allowable time and cost. The fact that the intrinsic viscosity [ eta ] of the allylamine copolymer is 0.03dl/g or more means that the monoallylamine-based monomer a and the ethylenically unsaturated monomer b can be highly copolymerized. That is, the molecular weight and/or the degree of polymerization can be indirectly evaluated by measuring the intrinsic viscosity [ η ].
The intrinsic viscosity [. Eta. ] of the allylamine-based copolymer is preferably 0.06 to 0.40dl/g, and particularly preferably 0.09 to 0.22dl/g.
The intrinsic viscosity [ eta ] of the allylamine-based copolymer can be measured by a capillary viscometer such as an Ubbelohde viscometer.
The viscosity of the allylamine (co) polymer can be suitably adjusted by adjusting the kind and composition of essential and arbitrary monomers, the temperature, time and pressure in the polymerization step, and the kind and amount of the radical initiator used in the polymerization step.
The allylamine copolymer of the present invention may contain a constituent unit a derived from a monoallylamine-based monomer a and a constituent unit B derived from an ethylenically unsaturated monomer B at a predetermined molar ratio, and may contain or may not contain other constituent units.
The proportion of the constituent unit a derived from the monoallylamine-based monomer a and the constituent unit B derived from the ethylenically unsaturated monomer B in the allylamine-based copolymer is not particularly limited, but is preferably 50 to 100 mol%, and more preferably 80 to 100 mol%.
When the ratio of the constituent unit a derived from the monoallylamine-based monomer a to the constituent unit B derived from the ethylenically unsaturated monomer B is within the above range, excellent characteristics such as reactivity, dispersibility, and the like can be more easily achieved.
The composition of the allylamine copolymer represented by the ratio of the constituent unit a derived from the monoallylamine-based monomer a to the constituent unit B derived from the ethylenically unsaturated monomer B can be suitably adjusted by the polymerization conditions, particularly the composition of the monomers to be polymerized.
Monoallylamine monomer a
The constituent unit A of the allylamine (co) polymer of the present invention as an essential constituent unit is derived from a monoallylamine-based monomer a.
The monoallylamine-based monomer a may be a compound having a monoallylamine structure, and is preferably a monoallylamine compound having a structure represented by the following general formula (I) or an addition salt thereof.
(in the formula, R 1 And R 2 Each of which is the same or different and represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms. )
In suitable compounds of the above formula (I), R 1 And R 2 The alkyl group having 1 to 12 carbon atoms in the (B) may be either linear or branched, or may be an aralkyl group. Examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, benzyl and the like. Examples of the cycloalkyl group having 5 to 6 carbon atoms include, but are not limited to, cyclopentyl and cyclohexyl.
Examples of suitable monoallylamine-based monomers represented by the above general formula (I) include: monoallylamine, N-methylallylamine, N-ethylallylamine, N-N-propylallylamine, N-isopropylallylamine, N-N-butylallylamine, N-isobutylallylamine, N-tert-butylallylamine, N-hexylallylamine, N-cyclohexylallylamine, N-dimethylallylamine, N-diethylallylamine, N-dipropylallylamine, N-dibutylallylamine, etc., but are not limited thereto.
Among them, monoallylamine is particularly preferable.
The addition salts of these suitable monoallylamine-based compounds are not particularly limited, and examples thereof include: hydrochloride, sulfate, phosphate, nitrate, sulfite, phosphite, nitrite, hydrobromide, acetate, amide sulfate, methanesulfonate, trifluoroacetate, p-toluenesulfonate and the like, but are not limited thereto.
Among them, hydrochloride, sulfate, phosphate, and amide sulfate are preferable, and hydrochloride, sulfate, phosphate, and amide sulfate of monoallylamine are particularly preferable.
In the present invention, the monoallylamine-based monomer a may be used alone in 1 kind or in combination with 2 or more kinds. The use of 1 monoallylamine-based monomer a alone is generally advantageous from the viewpoint of cost and ease of control of the polymerization step, and the use of 2 or more monoallylamine-based monomers a in combination is generally advantageous from the viewpoint of imparting desired properties to the copolymer.
Ethylenically unsaturated monomers b
The ethylenically unsaturated monomer b copolymerizable with the monoallylamine-based monomer a is not particularly limited, and a compound having at least 1 ethylenically unsaturated group copolymerizable with the monoallylamine-based monomer a can be suitably used.
Preferred examples of the ethylenically unsaturated monomer b include: examples of the monomer include, but are not limited to, carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid, and carboxylic acid monomers such as acrylonitrile, vinyl acetate, vinyl chloride, methacrylonitrile, styrene, acrylamide, methyl vinyl ketone, methyl vinyl ether, 4-vinylpyridine, N-vinylpyrrolidone, vinyl isocyanate, acrolein, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
Among them, acrylic acid and methacrylic acid are particularly preferable.
In the present invention, the monoallylamine-based monomer a may be used alone in 1 kind or in combination with 2 or more kinds. The use of 1 monoallylamine-based monomer a alone is generally advantageous from the viewpoint of cost and ease of control of the polymerization step, and the use of 2 or more monoallylamine-based monomers a in combination is generally advantageous from the viewpoint of imparting desired properties to the copolymer.
Method for producing allylamine copolymer
A method for producing an allylamine copolymer according to another embodiment of the present invention is a method for producing an allylamine copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, and includes a step of dropping the ethylenically unsaturated monomer b into an aqueous solution of the monoallylamine-based monomer a. By this step, monoallylamine-based monomers a and ethylenically unsaturated monomers b having different polymerizability can be polymerized in water at a high yield, and an allylamine-based copolymer having a desired composition and polymerization degree can be produced with practical efficiency and at a low cost.
The mechanism by which the above advantageous effect is obtained by the step of dropping the aqueous solution of the ethylenically unsaturated monomer into the aqueous solution of the monoallylamine-based monomer a is not clear, but is presumed to be as follows: the relatively low-polymerizability monoallylamine-based monomer a can be polymerized always in a large excess amount by diluting the relatively high-polymerizability ethylenically unsaturated monomer b into a certain aqueous solution and dropping it into the relatively low-polymerizability monoallylamine-based monomer a in the aqueous solution.
The temperature at which the step of dropping the aqueous solution of the ethylenically unsaturated monomer into the aqueous solution of the monoallylamine-based monomer a is carried out is not particularly limited, but is preferably carried out at a temperature in the range of 0 to 100 ℃, and particularly preferably at a temperature in the range of 50 to 65 ℃. The pressure at this time is also not particularly limited, and is preferably carried out at a pressure close to atmospheric pressure in view of cost and the like.
In the step of dropping the aqueous solution of the ethylenically unsaturated monomer b into the aqueous solution of the monoallylamine-based monomer a, a polymerization initiator is preferably used in order to accelerate the copolymerization reaction. The kind of the polymerization initiator is not particularly limited, and for example, a commonly used radical polymerization initiator can be used. The radical polymerization initiator is an initiator which generates radicals by heat or a reducing substance to initiate addition polymerization of a polymerizable monomer, and includes water-soluble, water-dispersible or oil-soluble persulfate, peroxide, azo-bis compound, and the like. Among them, water-soluble or water-dispersible azobis compounds are preferable, and 2,2 '-azobis (2-methylpropyl) dihydrochloride, dimethyl 2,2' -azobis (2-methylpropionate), and the like can be suitably used.
The time for carrying out the above-mentioned step is not particularly limited, but from the viewpoint of maintaining a large excess of the monoallylamine-based monomer a and stably carrying out the polymerization reaction, the aqueous solution of the ethylenically unsaturated monomer b is preferably dropped for 5 to 12 hours, particularly preferably 6 to 8 hours.
The amount and ratio of the monoallylamine-based monomer a and the ethylenically unsaturated monomer b to be supplied to the step of dropping the aqueous solution of the ethylenically unsaturated monomer b into the aqueous solution of the monoallylamine-based monomer a are not particularly limited, and the molar ratio of the monoallylamine-based monomer a to the ethylenically unsaturated monomer b is preferably 1:5 to 40:1, particularly preferably 1:3 to 20:1, more preferably 2:3 to 20:1. by supplying the monoallylamine-based monomer a and the ethylenically unsaturated monomer b in the above molar ratio, an allylamine-based copolymer having a desired composition can be efficiently produced.
The concentration of the monoallylamine-based monomer a and the concentration of the ethylenically unsaturated monomer b in the aqueous solution in the above step are not particularly limited, but are preferably a concentration of a certain value or less from the viewpoint of stable and uniform copolymerization or the like, and are preferably a concentration of a certain value or more from the viewpoint of polymerization efficiency or the like. More specifically, the concentration of the monoallylamine-based monomer a is preferably 4.0X 10 -3 ～6.5×10 -3 mol/g, particularly preferably 4.5X 10 -3 ～6.3×10 -3 mol/g. The concentration of the ethylenically unsaturated monomers b is preferably 10X 10 -3 ～20×10 -3 mol/g, particularly preferably 10X 10 -3 ～15×10 -3 mol/g。
The amount of the polymerization initiator used is not particularly limited, and when a water-soluble or water-dispersible azobis compound is used as the polymerization initiator, the polymerization initiator is preferably used in an amount of 1.0 to 10.0mol%, particularly preferably 2.0 to 5.0mol%, based on the total amount of the monoallylamine-based monomer a and the ethylenically unsaturated monomer b.
Preferred embodiments of the allylamine-based copolymer obtained by this production method are the same as those described for the allylamine-based copolymer of the present invention. Therefore, the composition of the allylamine copolymer obtained by this production method is: the molar ratio A/B of the constituent unit A derived from the monoallylamine-based monomer a to the constituent unit B derived from the ethylenically unsaturated monomer B is preferably from 0.4 to 25, more preferably from 0.4 to 15, still more preferably from 0.5 to 12, and particularly preferably from 0.6 to 10. The preferred molecular weight, intrinsic viscosity, and the like are the same as those described above for the allylamine copolymer of the present invention.
In a method for producing an allylamine copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer B, by employing a step of dropping an aqueous solution of the ethylenically unsaturated monomer B into an aqueous solution of the monoallylamine-based monomer a, the difference between the monomer composition (the molar ratio of the monoallylamine-based monomer a to the ethylenically unsaturated monomer B supplied to the step) to be fed and the composition of the copolymer (the molar ratio of the constituent unit a derived from the monoallylamine-based monomer a to the constituent unit B derived from the ethylenically unsaturated monomer B in the obtained allylamine-based copolymer) is reduced, and the composition of the copolymer can be easily and accurately controlled. Whether the copolymer composition can be easily and accurately controlled by the monomer composition of the feed can be evaluated by the following method: for example, the difference is preferably as small as possible when "the molar ratio a/(a + B) of the constituent unit a in the total of the constituent unit a and the constituent unit B in the obtained allylamine copolymer" is compared with "the molar ratio a/(a + B) of the monoallylamine monomer a supplied to the step in the total of the monoallylamine monomer a and the ethylenically unsaturated monomer B supplied to the step". More specifically, the molar ratio a/(a + B) in the copolymer is preferably ± 25% or less, more preferably ± 15% or less, of the molar ratio a/(a + B) in the feed composition.
In the method for producing an allylamine copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, the step of dropping an aqueous solution of the ethylenically unsaturated monomer b into an aqueous solution of the monoallylamine-based monomer a is employed, whereby the monomers a and b supplied to the polymerization step can be copolymerized without waste, and the allylamine copolymer can be produced at a high yield.
In the above production method, the yield of the feed is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
In addition, by using the above-mentioned production method, not only the yield is improved, but also the production of the following substances is suppressed: the residual monomers not involved in the copolymerization are homopolymers obtained by polymerizing only one monomer, particularly homopolymers of a residual monomer of a monoallylamine-based monomer a having a relatively low reactivity and homopolymers of an ethylenically unsaturated monomer b having a relatively high reactivity.
The amount of the monoallylamine-based monomer a remaining after the polymerization step is preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less of the amount of the monoallylamine-based monomer a supplied to the polymerization step.
Further, the amount of the homopolymer of the ethylenically unsaturated monomer b present after the polymerization step is preferably 10% by weight or less, particularly preferably 5% by weight or less, of the amount of the ethylenically unsaturated monomer b supplied to the polymerization step. In addition, "the homopolymer of the ethylenically unsaturated monomer b is substantially absent" can be confirmed by the fact that the product containing the allylamine-based copolymer obtained in the polymerization step is water-soluble or water-dispersible at pH2, 7 and 12.
The product of the step of copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer B generally includes an allylamine-based copolymer having a constituent unit a derived from the monoallylamine-based monomer a and a constituent unit B derived from the ethylenically unsaturated monomer B, and further, in some cases, a composition further including: a homopolymer obtained by polymerizing only one of the unimopolymer monoallylamine-based monomer a and the ethylenically unsaturated monomer b, particularly the monoallylamine-based monomer a having a relatively low reactivity, and a homopolymer obtained by polymerizing only one of the monomers, particularly the ethylenically unsaturated monomer b having a relatively high reactivity. By employing the step of dropping the aqueous solution of the ethylenically unsaturated monomer b into the aqueous solution of the monoallylamine-based monomer a, the yield of the desired allylamine-based copolymer can be improved, the amount of residual monomer can be reduced, and the formation of a homopolymer can be suppressed.
As a result, the content of components other than the desired allylamine copolymer (allylamine copolymer having a constituent unit A derived from a monoallylamine-based monomer a and a constituent unit B derived from an ethylenically unsaturated monomer B, wherein the molar ratio of the constituent unit A/the constituent unit B is from 0.4 to 25) in the composition as a product of the process can be reduced. The content of components other than the desired allylamine-based copolymer is preferably 10% by weight or less.
In addition, the content of unreacted monoallylamine-based monomer a and ethylenically unsaturated monomer b in the composition is reduced. The content of the unreacted monoallylamine-based monomer a and the ethylenically unsaturated monomer b is preferably 15% by weight or less, and more preferably 10% by weight or less.
Use of
The allylamine copolymer of the present invention is a copolymer of a monoallylamine-based monomer and an ethylenically unsaturated monomer having a desired composition and degree of polymerization, which cannot be produced by the prior art, exhibits water solubility or water dispersibility over a wide pH range, and is suitable for use in applications such as dispersants, reagents for ink-jet printing, adhesives, reagents for paper making, antistatic agents, coatings, wastewater treatment agents, anchor coating agents, synthetic resin films, dye fixing agents, or molding resins.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.
In the following examples/comparative examples, physical properties and characteristics were evaluated in the following manner.
(reprecipitation yield)
The reprecipitation yield is defined by the following formula.
Herein, the reprecipitation concentration was measured by the following method.
About 2g of the polymer aqueous solution was collected, and the weight (A) of the sample was measured. Then, the mixture was added to about 500ml of a solvent to precipitate and precipitate a polymer. Subsequently, the precipitate was filtered off using a glass filter. Subsequently, the solid polymer thus filtered was dried at 50 ℃ for 12 hours in a vacuum dryer. Finally, the weight of the dried precipitate (B) was measured. The reprecipitation concentration (%) was calculated according to the following formula.
The solid content concentration was measured by the following method.
About 2g of the polymer aqueous solution was collected, and the weight (C) of the sample was measured. Drying in a hot air dryer at 120 ℃ for 2 hours. The weight (D) after drying was measured. The solid content concentration was calculated according to the following formula.
(yield of feed)
From the amount of the fed material and the reprecipitation yield, it was calculated according to the following formula.
(amount of residual monomer)
The amount of residual monomer detected as an impurity was determined by gas chromatography. The amount of residual monomer was determined using a SHIMADZU gas chromatograph GC-2014, and helium was used as a carrier gas. The sample injection part and the hydrogen ion detector (FID) were set to 250 ℃, the column was set to 110 ℃, the linear velocity in the carrier gas was set to 40cm per second, and 1. Mu.L of the sample solution was injected at a split ratio of 1/20. The measurement was carried out using a column DB-1 (manufactured by Agilent technologies, ltd., length of 30m, inner diameter of 0.32mmID, liquid phase thickness of 3 μm). The temperature program of the column oven is as follows: held at 110 ℃ for 5 minutes, then warmed to 200 ℃ at 10 ℃/minute, then to 280 ℃ at 20 ℃/minute, and then held for 10 minutes.
(copolymerization ratio)
The copolymerization ratio was analyzed by measuring the amounts of a constituent unit A derived from a monoallylamine-based monomer a such as allylamine hydrochloride and a constituent unit B derived from an ethylenically unsaturated monomer B such as methacrylic acid, which constitute the copolymer, by elemental analysis.
The elemental analysis was performed in a CHN mode using a Perkin Elmer 2400I CHNS/O full-automatic elemental analysis apparatus. Helium was used as the carrier gas. The measurement was carried out by the following method: a solid sample is measured in a tin capsule, the solid sample is placed in a combustion tube, the sample is combusted in pure oxygen at a combustion temperature of 1800 ℃ or higher, each measurement component is detected by head-on chromatography using a separation column and a thermal conductivity detector, and the content of each element is quantified using a calibration coefficient.
(intrinsic viscosity of Polymer [ eta ])
The intrinsic viscosity [ eta ] of the polymer is represented by the following general formula.
η sp Specific viscosity and c is volume concentration (g/dl). In the formula, [ eta ]]Represents a value obtained by extrapolating c to 0.
As a specific method, the polymer was dissolved in 0.1N NaCl aqueous solution, 4 kinds of solutions having different concentrations of 0.25g/dl, 0.50g/dl, 0.75g/dl and 2.00g/dl were prepared, the solutions were adjusted to 30 ℃, and then the viscosity was measured by an Ubbelohde viscometer, and the concentration was extrapolated to 0, thereby obtaining the intrinsic viscosity [ η ].
(Water-soluble, water-dispersible at pH2, 7 and 12)
The presence or absence of water solubility and water dispersibility at each pH was determined by dissolving the allylamine copolymer in water at a concentration of 0.5 wt% at 25 ℃, adjusting the pH to 2.0, 7.0, and 12.0 using a 1N NaOH solution, and visually observing the formation of a precipitate.
(example 1)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b 1:
1
a300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 32.78g of distilled water and 0.5mol of allylamine hydrochloride. In addition, 100.0g of distilled water and 0.5mol of methacrylic acid were mixed in a 200ml beaker, and 2.0mol% based on the monomer (total of allylamine hydrochloride and methacrylic acid)Amount of sodium hypophosphite. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of an initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) relative to the monomer was added, followed by dropwise addition of an aqueous methacrylic acid solution from a dropping funnel to initiate polymerization. Methacrylic acid was added dropwise over 7 hours, and while adding 0.5mol% of the initiator V-50 to the monomer directly to the reaction system every 2 hours, the total was 4 times. After 24 hours, the polymerization was terminated to give a yellow, transparent, highly viscous solution. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 100.93%. Further, the yield calculated from the amount of the fed monomer was 97.34%. The peak (1700 cm) derived from the methacrylic acid monomer was confirmed by FT-IR measurement of the reprecipitated matter -1 、1155cm -1 、3000cm -1 ) And the peak from allylamine hydrochloride monomer (1155 cm) -1 、3000cm -1 )。
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 2)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b 3:
1
a300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 0.90mol of allylamine hydrochloride. In addition, 60.01g of distilled water and 0.30mol of methacrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) relative to the monomer (total of allylamine hydrochloride and methacrylic acid) was added, followed by dropwise addition of an aqueous methacrylic acid solution by a micro-tube pump to initiate polymerization. Methacrylic acid was added dropwise over 12 hours. Meanwhile, the initiator V-50 was directly added to the reaction system, 1mol% was added 3 hours after the start of the polymerization, 0.5mol% was added 20 hours after the start of the polymerization, and the polymerization reaction was terminated 30 hours after the end of the polymerization, whereby a yellow transparent highly viscous solution was obtained. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 104.00%, and the yield calculated from the feed was 100.82%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 3)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b 5:
1
a300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 1.00mol of allylamine hydrochloride. Further, 17.04g of distilled water and 0.20mol of methacrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 0.5mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) was added to the monomer (total of allylamine hydrochloride and methacrylic acid), and then an aqueous methacrylic acid solution was added through a dropping funnel to initiate polymerization. Methacrylic acid was added dropwise over 12 hours. Meanwhile, the initiator V-50 was added directly to the reaction system, and 1.0mol% was added 4 hours after the start of the polymerization and 1.0mol% was added 20 hours after the start of the polymerization. The polymerization was terminated after 30 hours to give a yellow, transparent, highly viscous solution. The yield was confirmed by the reprecipitation operation using IPA, and the reprecipitation yield was 96.49%, and the yield calculated from the charge was 98.93%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 4)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b
10：1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 1.20mol of allylamine hydrochloride. In addition, 15.39g of distilled water and 0.12mol of methacrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) was added with respect to the monomer (total of allylamine hydrochloride and methacrylic acid), and then an aqueous methacrylic acid solution was added through a dropping funnel to initiate polymerization. Methacrylic acid was added dropwise over 6 hours, while directly adding the initiator V-50 to the reaction system every 3 hours, 1.0mol% to the monomer 1 time, 1.5mol% to the monomer 1 time, 2 times in total. The polymerization was terminated after 24 hours to obtain a yellow transparent highly viscous solution. The yield was confirmed by the reprecipitation operation using IPA, and the reprecipitation yield was 100.50%, and the yield calculated from the feed was 100.02%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 5)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b
15：1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 1.20mol of allylamine hydrochloride. In addition, 10.26g of distilled water and 0.08mol of methacrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 0.5mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) based on the monomers (total of allylamine hydrochloride and methacrylic acid) was added, and then an aqueous methacrylic acid solution was added through a dropping funnel to initiate polymerization. Methacrylic acid was added dropwise over 6 hours, while 0.5mol% of the initiator V-50 with respect to the monomer was directly added to the reaction system every 3 hours for 2 times. The polymerization was terminated after 24 hours to obtain a yellow transparent highly viscous solution. The yield was confirmed by the reprecipitation operation using IPA, and the reprecipitation yield was 98.91%, and the yield calculated from the feed was 96.57%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 6)
Allylamine hydrochloride/methacrylic acid co-polymerPolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b
20：1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 1.40mol of allylamine hydrochloride. In addition, 8.98g of distilled water and 0.07mol of methacrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 0.5mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) was added to the monomer (total of allylamine hydrochloride and methacrylic acid), and then an aqueous methacrylic acid solution was added through a dropping funnel to initiate polymerization. Methacrylic acid was added dropwise over 6 hours, while 1.0mol% of the initiator V-50 with respect to the monomer was directly added to the reaction system every 3 hours for 2 times. The polymerization was terminated after 24 hours to give a yellow, transparent, highly viscous solution. The yield was confirmed by the reprecipitation operation using IPA, and the reprecipitation yield was 99.72%, and the yield calculated from the feed was 98.65%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 7)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomer b 2:
3
a300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 21.94g of distilled water and 0.3mol of allylamine hydrochloride. In a 200ml beaker, 115.83g of distilled water, 0.45mol of methacrylic acid and 4.0mol% of sodium hypophosphite with respect to the monomer were mixed. The internal temperature in the separable flask was heated to 60 ℃ and 0.5mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) relative to the monomer (total of allylamine hydrochloride and methacrylic acid) was added, and then an aqueous methacrylic acid solution was added by a quantitative pump to initiate polymerization. Methacrylic acid was added dropwise over 10 hours, and then 1.0mol% of the initiator V-50 based on the monomer was added directly to the reaction system after 3 to 7 hours. The polymerization was terminated after 30 hours to give a yellow, transparent, highly viscous solution. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 98.06%, and the yield calculated from the charge was 96.35%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 8)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b 1:1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 28.90g of distilled water and 0.4mol of allylamine hydrochloride. In addition, 60.05g of distilled water and 0.4mol of acrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) was added with respect to the monomer (total of allylamine hydrochloride and acrylic acid), and then an aqueous acrylic acid solution was added through a dropping funnel to initiate polymerization. Acrylic acid was added dropwise over 7 hours, and during this time, 0.5mol% of the initiator V-50 based on the monomer was added directly to the reaction system 3 times at 2-hour intervals. The polymerization reaction was terminated after 24 hours to obtain an orange transparent solution. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 104.07%, and the yield calculated from the feed was 101.42%. The peak (1700 cm) derived from the acrylic acid monomer was confirmed by FT-IR measurement of the reprecipitate -1 、1155cm -1 、3000cm -1 ) And the peak from allylamine hydrochloride monomer (1155 cm) -1 、3000cm -1 )。
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 9)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomer b 3:1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 0.6mol of allylamine hydrochloride. In addition, 61.90g of distilled water and 0.2mol of acrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) based on the monomers (total of allylamine hydrochloride and acrylic acid) was added, and then an aqueous acrylic acid solution was added through a dropping funnel to initiate polymerization. Acrylic acid was added dropwise over 7 hours, and 1.0mol% of the initiator V-50 based on the monomer was added directly to the reaction system 2 times at intervals of 3 hours. The polymerization reaction was terminated after 24 hours to obtain an orange transparent solution. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 91.17%, and the yield calculated from the charge was 89.31%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 10)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b 5:1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 1.0mol of allylamine hydrochloride. Further, 37.17g of distilled water and 0.2mol of acrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) was added with respect to the monomer (total of allylamine hydrochloride and acrylic acid), and then an aqueous acrylic acid solution was added through a dropping funnel to initiate polymerization. Acrylic acid was added dropwise over 7 hours, and 1.0mol% of the initiator V-50 based on the monomer was added directly to the reaction system 2 times at intervals of 3 hours. The polymerization reaction was terminated after 24 hours to obtain an orange transparent solution. The yield was confirmed by the reprecipitation operation using IPA, and the reprecipitation yield was 97.37%. The yield calculated from the feed was 95.24%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 11)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomer b 2:3
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 10.55g of distilled water and 0.40mol of allylamine hydrochloride. In addition, 69.49g of distilled water and 0.60mol of acrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 0.5mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) relative to the monomer (total of allylamine hydrochloride and acrylic acid) was added, and then an aqueous acrylic acid solution was added by a quantitative pump to initiate polymerization. Acrylic acid was added dropwise over 12 hours, and 1.0mol% of the initiator V-50 based on the monomer was added directly to the reaction system over 3 to 18 hours. The polymerization reaction was terminated after 30 hours to obtain an orange transparent solution. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 105.42%, and the yield calculated from the feed was 106.13%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 12)
Allylamine amide sulfate/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b
The ratio is 1:1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 55.63g of distilled water and 0.3mol of allylamine amide sulfate. In addition, 60.0g of distilled water, 0.3mol of methacrylic acid, and sodium hypophosphite in an amount of 2.0mol% relative to the monomer (total of allylamine amide sulfate and methacrylic acid) were mixed in a 200ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) relative to the monomer was added, and then an aqueous methacrylic acid solution was added through a dropping funnel to initiate polymerization. Dropping methacrylic acid water in 7 hoursWhile the solution was being added, 1.0mol% of the initiator V-50 relative to the monomer was added directly to the reaction system 2 times at intervals of 3 hours. The polymerization was terminated after 24 hours to obtain a yellow transparent highly viscous liquid. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 98.03%. In addition, the yield calculated from the feed was 97.55%. The peak (1700 cm) derived from the methacrylic acid monomer was confirmed by FT-IR measurement of the reprecipitated matter -1 、1155cm -1 、3000cm -1 ) And the peak from allylamine amide sulfate monomer (1155 cm) -1 、3000cm -1 )。
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 13)
Allylamine amide sulfate/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b
The ratio 3:1
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 77.75g of distilled water and 0.45mol of allylamine amide sulfate. In addition, 19.24g of distilled water, 0.15mol of methacrylic acid, and sodium hypophosphite in an amount of 1.0mol% relative to the monomer (total of allylamine amide sulfate and methacrylic acid) were mixed in a 100ml beaker. The internal temperature of the separable flask was heated to 60 ℃ and 1.0mol% of an initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) relative to the monomer was added, and then an aqueous methacrylic acid solution was added through a dropping funnel to initiate polymerization. An aqueous methacrylic acid solution was dropped over 8 hours, and while 1.0mol% of the initiator V-50 based on the monomer was directly added to the reaction system every 3 hours, 2 times in total. The polymerization was terminated after 24 hours to obtain a yellow transparent highly viscous liquid. The yield was confirmed by the reprecipitation operation using acetone, and the reprecipitation yield was 94.72%. In addition, the yield calculated from the feed was 93.14%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
(example 14)
Allylamine amide sulfate/methacrylic acid copolymer, monoallylamine-based monomer a: ratio of ethylenically unsaturated monomers b
The ratio is 5:1
49.26g of distilled water and 0.7mol of allylamine amide sulfate were placed in a 300ml separable flask equipped with a stirrer, a thermometer and a condenser. In addition, 28.00g of distilled water and 0.14mol of methacrylic acid were mixed in a 100ml beaker. The internal temperature in the separable flask was heated to 60 ℃ and 1.0mol% of initiator V-50 (2, 2' -azobis (2-methylpropionamidine) dihydrochloride) relative to the monomer was added, and then an aqueous methacrylic acid solution was added through a dropping funnel to initiate polymerization. An aqueous methacrylic acid solution was dropped over 8 hours, and while 1.0mol% of the initiator V-50 based on the monomer was directly added to the reaction system every 3 hours, 2 times in total. The polymerization was terminated after 24 hours to obtain a yellow transparent highly viscous liquid. The yield was confirmed by the reprecipitation operation using IPA, and the reprecipitation yield was 96.22%. In addition, the yield calculated from the feed was 98.93%.
The results are shown in Table 1.
The evaluation results of water solubility and water dispersibility at pH2, 7 and 12 are shown in table 2.
Comparative example 1
Production of allylamine amide sulfate/acrylic acid copolymer of the prior art, monoallylamine-based monomer a: in the olefinic family
Ratio of saturated monomers b 2:3
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 99.62g of methanol, 0.3mol of allylamine amide sulfate and 0.45mol of acrylic acid, and the internal temperature was heated to 50 ℃. After the internal temperature was stabilized, 2.5mol% of initiator V-601 (2, 2' -azobis (2-methylpropionate) based on the monomer (the total of allylamine amide sulfate and acrylic acid) was added, and further 2.5mol% of the initiator V-601 based on the monomer was added after 24 hours, and the polymerization reaction was terminated after 48 hours. The white precipitate precipitated at the bottom of the flask was filtered to obtain 150.31g of a highly viscous yellow turbid liquid. The homopolymer of acrylic acid was removed by a reprecipitation operation using IPA to obtain an allylamine amide sulfate/acrylic acid copolymer as a filtrate. The reprecipitation yield of the resulting copolymer was 67.08%, and the yield calculated from the feed was 50.91%. In addition, it is insoluble in water and dissolves in water only under highly alkaline specific pH conditions.
The results are shown in tables 1 and 2.
Comparative example 2
Prior art manufacture of allylamine amide sulfate/acrylic acid copolymers, monoallylamine-based monomer a: of olefinic type
Ratio of saturated monomers b 2:3
A300 ml separable flask equipped with a stirrer, a thermometer and a condenser was charged with 28.78g of methanol and 0.3mol of allylamine amide sulfate. In addition, 75.34g of methanol and 0.45mol of acrylic acid were mixed in a 100ml beaker. After the internal temperature was raised to 50 ℃ and stabilized, 2.5mol% of an initiator V-601 (2, 2' -azobis (2-methylpropionate) dimethyl ester was added to the monomer (the total of allylamine amide sulfate and acrylic acid), and then a methanol solution of an acrylic monomer was added dropwise thereto by means of a metering pump to initiate polymerization. An acrylic monomer was added dropwise over 8 hours, and 24 hours after the start of the polymerization, 2.5mol% of an initiator V-601 based on the monomer was directly added to the reaction system, followed by further reaction for 48 hours. After the reaction was completed, a white precipitate precipitated at the bottom of the flask was filtered to obtain 106.00g of a highly viscous yellow turbid solution. The homopolymer of acrylic acid was removed by a reprecipitation operation using IPA to obtain an allylamine amide sulfate/acrylic acid copolymer as a filtrate. The reprecipitation yield of the resulting copolymer was 68.45%, and the yield calculated from the charge was 35.08%. In addition, it is insoluble in water and dissolves in water only under highly alkaline specific pH conditions.
The results are shown in tables 1 and 2.
TABLE 2
Industrial applicability
The present invention can provide a copolymer of a monoallylamine-based monomer and an ethylenically unsaturated monomer having a desired composition and degree of polymerization at a practical efficiency and cost, achieves a significant technical effect of high practical value, and has high availability in various industrial fields including the chemical industry, the paper industry, and the electrical and electronic industry.
Claims (6)
1. A process for producing an allylamine copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, which comprises a step of dropping an aqueous solution of the ethylenically unsaturated monomer b into an aqueous solution of the monoallylamine-based monomer a during polymerization,
the monoallylamine-based monomer a described above contains at least 1 monomer selected from the group consisting of monoallylamine hydrochloride, monoallylamine sulfate, monoallylamine phosphate and monoallylamine amide sulfate,
the above ethylenically unsaturated monomer b comprises (meth) acrylic acid,
the allyl amine copolymer produced has a molar ratio A/B of the constituent unit A derived from the monoallylamine-based monomer a to the constituent unit B derived from the ethylenically unsaturated monomer B of 0.4 to 25,
the intrinsic viscosity [ eta ] is 0.03dl/g or more.
2. The method according to claim 1, wherein the step is performed at a temperature ranging from 0 to 100 ℃.
3. The method according to claim 1 or 2, wherein the molar ratio of the monoallylamine-based monomer a to the ethylenically unsaturated monomer b supplied to the above step is 1:5 to 40:1.
4. the method according to claim 1 or 2, wherein the molar ratio a/(a + B) of the constituent unit a to the total of the constituent unit a and the constituent unit B in the allylamine copolymer is within a range of a/(a + B) ± 25% of the molar ratio of the monoallylamine-based monomer a supplied to the step to the total of the monoallylamine-based monomer a and the ethylenically unsaturated monomer B supplied to the step.
5. The process according to claim 1 or 2, wherein the yield of the allylamine-based copolymer from the feed is 70% by weight or more.
6. The method according to claim 1 or 2, wherein the amount of the monoallylamine-based monomer a remaining unpolymerized after the above-mentioned step is 70% by weight or less of the amount of the monoallylamine-based monomer a supplied to the above-mentioned step.
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| EP0145220A2 (en) * | 1983-11-10 | 1985-06-19 | Nitto Boseki Co., Ltd. | Process for producing polymers of monoallylamine |
| JPH0379610A (en) * | 1989-08-23 | 1991-04-04 | Nitto Boseki Co Ltd | Amphoteric polymer and production thereof |
| JP2001106736A (en) * | 1999-10-06 | 2001-04-17 | Nitto Boseki Co Ltd | Production process for allylamine copolymer |
| JP2002293842A (en) * | 2001-03-30 | 2002-10-09 | Nitto Boseki Co Ltd | Allylamine-allylsulfonic acid-based copolymer, its production method and use |
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| JPS60104107A (en) * | 1983-11-10 | 1985-06-08 | Nitto Boseki Co Ltd | Production of monoallylamine polymer |
| KR101776369B1 (en) * | 2014-10-10 | 2017-09-08 | 연세대학교 산학협력단 | Polymer having high adsorption ability for metal ions and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0145220A2 (en) * | 1983-11-10 | 1985-06-19 | Nitto Boseki Co., Ltd. | Process for producing polymers of monoallylamine |
| JPH0379610A (en) * | 1989-08-23 | 1991-04-04 | Nitto Boseki Co Ltd | Amphoteric polymer and production thereof |
| JP2001106736A (en) * | 1999-10-06 | 2001-04-17 | Nitto Boseki Co Ltd | Production process for allylamine copolymer |
| JP2002293842A (en) * | 2001-03-30 | 2002-10-09 | Nitto Boseki Co Ltd | Allylamine-allylsulfonic acid-based copolymer, its production method and use |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI805696B (en) | 2023-06-21 |
| TW201936677A (en) | 2019-09-16 |
| WO2019163737A1 (en) | 2019-08-29 |
| JPWO2019163737A1 (en) | 2021-02-04 |
| JP7276669B2 (en) | 2023-05-18 |
| KR20200124660A (en) | 2020-11-03 |
| CN111757898A (en) | 2020-10-09 |
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