TW201936677A - Allylamine copolymer and method for producing the same - Google Patents

Abstract

Provided is an allylamine copolymer which is obtained by polymerizing a monoallylamine monomer and an ethylenically unsaturated monomer, said monomers having different polymerization properties, in water with high yield, and which has a desired composition and a desired polymerization degree. The above-described problem is solved by an allylamine copolymer which has a constituent unit A that is derived from a monoallylamine monomer a and a constituent unit B that is derived from an ethylenically unsaturated monomer b, and which has a (constituent unit A)/(constituent unit B) molar ratio of 0.4-25.

Description

Allylamine copolymer and method for producing the same

The present invention relates to an allylamine-based copolymer and a process for producing the same. More specifically, the present invention relates to a copolymer of a monoallylamine-based monomer and an ethylenically unsaturated monomer, which has a copolymer having a copolymerization composition which cannot be achieved by the prior art, and which can be efficiently obtained. A method of manufacturing a copolymer.

The allyl monomer, particularly the monoallylamine monomer, is considered to be deficient in the radical polymerization due to the repulsive linkage movement due to the resonance stability of the allyl radical. On the other hand, an ethylenically unsaturated single system such as (meth)acrylic acid is known as a monomer having high radical polymerizability. Therefore, the copolymer cannot be obtained by approximating the molar ratio of the two. When the two types of monomers are copolymerized in water, in the prior art, ethylene (meth)acrylic acid or the like having high radical polymerizability is distinguished by the polymerization property of the two monomers and the difference in polymerization rate. Polymerization of the unsaturated monomer is believed to result in the formation of a separate polymer.

As a method of copolymerizing a monoallylamine-based monomer and an ethylenically unsaturated monomer such as (meth)acrylic acid, addition of a hydrochloride of a monoallylamine-based monomer or the like has been proposed. The salt is reacted with (meth)acrylic acid in a methanol solvent (for example, Patent Document 1 is incorporated by reference).
However, in the method described in Patent Document 1, the yield of the monoallylamine hydrochloride/(meth)acrylic acid copolymer is 50% or less. Further, in this method, in order to simultaneously produce a monoallylamine hydrochloride individual polymer or a (meth)acrylic acid single polymer, it is necessary to carry out such troublesome work such as filtration and removal.
Further, according to the method described in Patent Document 1, the inventors of the present invention have a problem that the solubility of the obtained copolymer in water is lowered. The copolymer is a solution in which water is dissolved in water only in a certain pH range, and according to this, a copolymer of a desired composition is not actually obtained, and a single polymer of acrylic acid or a mixture of individual monomers of two monomers is substantially produced. The possibility is high.
Conventionally, in the copolymer of a monoallylamine-based monomer and an ethylenically unsaturated monomer, no practical synthesis method has been found.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] JP-A-2001-106736
[Non-patent literature]

[Non-Patent Document 1] Sawada Hideo and other four, Japan Oil Chemistry Society, Volume 46, No. 2 (1997), 191~203

[Problems to be solved by the invention]

As described above, in each of the prior art documents, it is reported that the monoallylamine hydrochloride/(meth)acrylic acid copolymer is synthesized by the synthesis method described in the literature, and in reality, the desired copolymer is not obtained. There is clear evidence that there is a problem that it is difficult to dissolve in water, low yield, etc., so it is necessary to obtain a desired synthesis method of the copolymer in a practical and high yield.
It is an object of the present invention to provide a monoallylamine-based monomer having a different polymerizability and an ethylenically unsaturated monomer which are polymerized in a good yield in water in view of the above-described limitations of the prior art. A method for producing a allylic amine copolymer having a composition and a degree of polymerization, and an allyl group-like copolymer thereof, which can be produced with practical efficiency and cost.

[Means for solving the problem]

In order to achieve the above-mentioned object, the inventors of the present invention have repeatedly studied the results of the research, and the ethylenically unsaturated monomer having a good polymerization property such as (meth)acrylic acid which is excellent in polymerizability in an aqueous solvent is dripped. Adding to a monoallylamine-based monomer, a copolymer of a monoallylamine-based monomer and an ethylenically unsaturated monomer can be easily produced under normal pressure and under heating conditions, and the copolymer is found. The present invention has been completed on the basis of the knowledge that the ratio of acrylic acid is large and water-soluble or water-dispersible.
That is, the system of the present invention,
[1] An allylamine-based 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, and a constituent unit A/constituting unit B The molar ratio is 0.4 to 25, and the above allylamine copolymer.

Further, the following [2] to [15] are each an embodiment or an excellent embodiment of the present invention.
[2] The allylamine-based copolymer described in [1], which is water-soluble or water-dispersible in pH 2, 7, and 12.
[3] The allylamine-based copolymer described in [1] or [2], having an intrinsic viscosity [η] of 0.03 (dl/g) or more.
[4] The monoallylamine-based monomer a is a monoallylamine hydrochloride, a monoallylamine sulfate, a monoallylamine phosphate, and a monoallylamine guanamine sulfate The at least one monomer selected from the group consisting of a salt, the allylamine-based copolymer according to any one of [1] to [3].
[5] The ethylenically unsaturated monomer is an allylamine-based copolymer according to any one of [1] to [4], which comprises (meth)acrylic acid.
[6] A composition comprising the allylamine-based copolymer according to any one of [1] to [5], an unreacted monoallylamine-based monomer a and an ethylenically unsaturated monomer b The content is the total amount of 15% by weight or less of the above composition.
[7] A method of producing an allylamine-based copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, and having the monoallylamine-based monomer a The step of dropping the aqueous solution of the ethylenically unsaturated monomer b into the aqueous solution, the above method.
[8] The above steps are carried out in a temperature range of 0 to 100 ° C, and the method described in [7].
[9] In the foregoing step, the molar ratio of the monoallylamine monomer a and the ethylenically unsaturated monomer b is 1:5 to 40:1, and the method described in [7] or [8] .
[10] In the allylamine-based copolymer produced, the constituent unit A derived from the monoallylamine-based monomer a and the constituent unit B derived from the ethylenically unsaturated monomer b The ratio A/B is a method described in any one of 0.4 to 25, [7] to [9].
[11] In the allylamine-based copolymer, the molar ratio A/(A+B) in which the constituent unit A occupies the total of the constituent unit A and the constituent unit B is supplied to the aforementioned single sheet in the aforementioned step. The allylamine monomer a occupies ±25% of the molar ratio a/(a+b) supplied to the total of the monoallylamine monomer a and the ethylenically unsaturated monomer b in the same step. The method described in any one of [7] to [10].
[12] The yield of the feed of the allylamine-based copolymer is 70% by weight or more, and the method according to any one of [7] to [11].
[13] The amount of the monoallylamine-based monomer a remaining in the unpolymerized step after the above step is 70% by weight or less based on the amount of the monoallylamine-based monomer a in the above step, [7]~ [12] The method described in any one of [12].
[14] A dispersant comprising the allylamine-based copolymer according to any one of [1] to [5], an inkjet printing agent, an adhesive, a papermaking agent, an antistatic agent, a coating material, A wastewater treatment agent, an anchor coating agent, a synthetic resin film, a dye fixing agent, or a molding resin.

[Effects of the Invention]

According to the present invention, a copolymer of a monoallylamine-based monomer having an intended composition and degree of polymerization and an ethylenically unsaturated monomer which cannot be produced by the prior art is provided. 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 of printing materials, adhesives, coatings and the like.
Further, by the production method of the present invention, a copolymer of a monoallylamine-based monomer and an ethylenically unsaturated monomer can be polymerized in an excellent yield in water to give an ally having a desired composition and degree of polymerization. The amide copolymer is produced at a practical efficiency and at a cost.

[Best Mode for Carrying Out the Invention]

Allylamine-based copolymer The present invention has an allylamine-based 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. The molar ratio of the constituent unit A/constituting unit B is 0.4 to 25, and the above allylamine-based copolymer.
In other words, the allylamine-based copolymer of the present invention contains the constituent unit A derived from the monoallylamine-based monomer a and the constituent unit B derived from the ethylenically unsaturated monomer b, and contains the specified mo. The ear ratio may be, or may be, a constituent unit other than the unit, or a constituent unit other than the unit.
In the allylamine-based copolymer of the present invention, the molar ratio of the constituent unit A/constituting unit B is from 0.4 to 25, which means that the monoallylamine-based monomer a and the ethylenically unsaturated monomer b are A wide range of homopolymers containing copolymerization, which is a copolymerization ratio which can be expected to be copolymerized, means that a copolymer which was not obtained by the prior art was obtained.
In the allylamine-based copolymer of the present invention, the molar ratio of the unit A/constituting unit B is preferably 0.4 to 15, more preferably 0.5 to 12, and preferably 0.6 to 10. The special features are more powerful and particularly excellent.
In the allylamine-based copolymer of the present invention, the molar ratio of the constituent unit A/composition unit B is measured by elemental analysis to determine a monoallylamine-based single sheet which constitutes a copolymer, an allylamine hydrochloride or the like. The amount of the constituent unit B derived from the constituent unit A derived from the body a and the ethylenically unsaturated monomer b such as methacrylic acid can be defined.

The allylamine-based copolymer of the present invention is preferably water-soluble or water-dispersible in pH 2, 7, and 12. Here, "water-soluble" means that the allylamine-based copolymer is dissolved in water to form a transparent solution, and "water-dispersible" means that the allylamine-based copolymer is dispersed in water (including dissolution). In some cases, residual undissolved solids are visible in size.
The above-mentioned water solubility or water dispersibility in pH 2, 7, and 12 means that the copolymer is water-soluble or water-dispersible in a wide pH range, and indirectly means that a desired composition (constitutive unit) can be obtained. A/Allylamine-based copolymer constituting the molar ratio of the unit B.
On the other hand, when a single polymer of an ethylenically unsaturated monomer such as a monoallylamine hydrochloride alone polymer or a (meth)acrylic acid alone polymer is mixed, it may be due to any of the above pHs. When an ionic complex or the like is formed and is insoluble in water, when it is insoluble in water at any of the above pHs, an allylamine-based copolymer having a desired composition cannot be obtained in a high yield, from the remaining ethylenically unsaturated monomer b The formation of a separate polymer of ethylenically unsaturated monomer b, or the possibility of forming other individual polymers. In this case, there is a concern that the trouble of the troublesome work of removing the individual polymer of the ethylenically unsaturated monomer b by filtration or the like is required.
The water solubility or water dispersibility in pH 2, 7, and 12 of the allylamine copolymer can be adjusted to pH 2 by dissolving the allylamine copolymer in water using an aqueous NaOH solution or the like. 7, 7, and 12, visually observed to determine the formation of precipitates.
The allylamine-based copolymer of the present invention is preferably water-soluble or water-dispersible in the range of pH 0 to 14, and particularly preferably water-soluble in the range of pH 0 to 14.

The molecular weight of the allylamine-based copolymer of the present invention is not particularly limited, and a (co)polymer having a suitable molecular weight can be suitably polymerized depending on the desired physical properties or use. When the molecular weight of the allylamine-based copolymer is such that it can be dissolved in a solution, it can be measured by a GPC method. Further, when the intrinsic viscosity [η] is measured, it can be indirectly evaluated.
The intrinsic viscosity [η] is preferably 0.03 dl/g or more from the viewpoint of having an appropriate viscosity for use in a dispersant, an adhesive, a coating material, or the like, and from practically allowing polymerization at an acceptable time and cost. In addition, the intrinsic viscosity [η] of the allylamine-based copolymer is 0.03 dl/g or more, which means that the monoallylamine-based monomer a and the ethylenically unsaturated monomer b can be made highly polymerizable. Perform copolymerization. That is, when the intrinsic viscosity [η] is measured, the molecular weight and/or the degree of polymerization can be indirectly evaluated.
The intrinsic viscosity [η] of the allylamine-based copolymer is preferably from 0.06 to 0.40 dl/g, particularly preferably from 0.09 to 0.22 dl/g.
The intrinsic viscosity [η] of the allylamine-based copolymer can be measured by, for example, a capillary viscometer such as a Ubbelohde viscometer.
The viscosity of the allylamine (co)polymer to adjust the type and composition of any monomer, the temperature, time and pressure in the polymerization step, the type and amount of the radical initiator used in the polymerization step, etc. Can be adjusted.

The allylamine-based copolymer of the present invention has a specified molar ratio of the constituent unit A derived from the monoallylamine-based monomer a and the constituent unit B derived from the ethylenically unsaturated monomer b. It is possible to have other constituent units or other constituent units.
The proportion of the constituent unit B derived from the constituent unit A derived from the monoallylamine-based monomer a and the ethylenically unsaturated monomer b is not particularly limited as long as it is contained in the allylamine-based copolymer. 50~100% of the mole is better, and 80~100% of the mole is better.
When the ratio of the constituent unit B derived from the constituent unit A derived from the monoallylamine-based monomer a and the ethylenically unsaturated monomer b is within the above range, excellent properties such as reactivity and dispersibility can be obtained. It is easier to implement on the next level.
The ratio of the constituent unit B derived from the constituent unit A derived from the monoallylamine-based monomer a and the ethylenically unsaturated monomer b is started, and the composition of the allylamine-based copolymer is determined by polymerization conditions. In particular, the composition of the monomer provided in the polymerization can be suitably adjusted.

Monoallylamine monomer a
The constituent unit A of the essential constituent unit of the allylamine (co)polymer of the present invention is derived from the monoallylamine-based monomer a.

The monoallylamine-based monomer a may be a compound having a monoallylamine structure, but has the following general formula (I)

(wherein R ¹ and R ² in the formula represent a mono-allyl group having a hydrogen atom of the same or different, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms; The amine compound, or an addition salt thereof, is preferred.

In a suitable compound represented by the above formula (I), the alkyl group having 1 to 12 carbon atoms in R ¹ and R ² may be either linear or branched, or may be an aralkyl group. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. , dodecyl, benzyl and the like. Further, examples of the cycloalkyl group having 5 to 6 carbon atoms include a cyclopentyl group and a cyclohexyl group, but are not limited thereto.

Examples of suitable monoallylamine-based monomers represented by the above general formula (I) include monoallylamine, N-methylallylamine, N-ethylallylamine, and Nn. -propylallylamine, N-isopropylallylamine, Nn-butylallylamine, N-isobutylallylamine, N-tert-butylallylamine, N- Hexylallylamine, N-cyclohexylallylamine, N,N-dimethylallylamine, N,N-diethylallylamine, N,N-dipropylallylamine N, N-dibutylallylamine or the like, but is not limited thereto.
Among them, monoallylamine is particularly preferred.

The addition salt of such a suitable monoallylamine-based compound is not particularly limited, and examples thereof include hydrochloride, sulfate, phosphate, nitrate, cesium sulfate, strontium phosphate, cerium nitrate, and hydrobromine. The acid salt, the acetate salt, the guanamine sulfate salt, the methanesulfonate salt, the trifluoroacetate salt, the p-toluenesulfonate salt, and the like are not limited thereto.
Among them, hydrochloride, sulfate, phosphate, and guanamine sulfate are preferred, and hydrochlorides, sulfates, phosphates, and guanamine sulfates of monoallylamine are particularly preferred.

In the present invention, the monoallylamine-based monomer a may be used alone or in combination of two or more types. The use of only one type of monoallylamine-based monomer a means that it is more advantageous in terms of cost or control difficulty in the polymerization step, and the use of a combination of two or more means that the copolymer is expected to be imparted. The point of nature is more favorable.

Ethylene unsaturated monomer b
Copolymerization with the monoallylamine-based monomer a, and the ethylenically unsaturated monomer b is not particularly limited, and at least one ethylenically unsaturated group may be suitably used, and may be co-polymerized with the monoallylamine-based monomer a. Polymerized compound.
Preferred examples of the ethylenically unsaturated monomer b include carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid, acrylonitrile, vinyl acetate, and vinyl chloride. Methacrylonitrile, styrene, acrylamide, methyl vinyl ketone, methyl vinyl ether, 4-vinyl pyridine, N-vinyl pyrrolidone, vinyl isocyanate, acrolein, methyl acrylate, ethyl acrylate , acryl propyl, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc., but is not limited thereto.
Among them, acrylic acid and methacrylic acid are particularly preferred.
In the present invention, the monoallylamine-based monomer a may be used alone or in combination of two or more types. The use of only one type of monoallylamine-based monomer a means that it is more advantageous at the point of cost or control difficulty of the polymerization step, and the use of a combination of two or more means that the copolymer is expected to be imparted. The point of nature is more favorable.

Method for producing allylamine-based copolymer The method for producing an allylamine-based copolymer according to another aspect of the present invention is to copolymerize a monoallylamine-based monomer a and an ethylenically unsaturated monomer b. The method for producing an allylamine-based copolymer has a step of dropping the ethylenically unsaturated monomer b into an aqueous solution of the monoallylamine-based monomer a. By using this step, the monoallylamine-based monomer a having different polymerizability and the ethylenically unsaturated monomer b can be polymerized in an excellent yield in water, and can be produced with practical efficiency and cost. An allylamine copolymer having a composition and a degree of polymerization.
The step of obtaining the above-described advantageous effects by the step of dropping the aqueous solution of the ethylenically unsaturated monomer in the aqueous solution of the monoallylamine-based monomer a is not understood, but it is presumed that higher polymerization property is obtained. The ethylenically unsaturated monomer b is diluted as an aqueous solution to drip the lower polymerizable monoallylamine monomer a to the lower polymerizable monoallylamine system. It is relevant that the monomer a is always polymerized under conditions of a large excess of ruthenium.

The temperature of the step of dropping the aqueous solution of the ethylenically unsaturated monomer into the aqueous solution of the monoallylamine-based monomer a is not particularly limited, but is preferably carried out at a temperature of from 0 to 100 ° C. It is particularly preferred to carry out in the temperature range of ~65 °C. There is no particular restriction on the pressure at that time, but it is better to perform near atmospheric pressure if cost is considered.
In the step of dropping the aqueous solution of the ethylenically unsaturated monomer b into the aqueous solution of the monoallylamine-based monomer a, it is preferred to use a polymerization initiator in order to promote the copolymerization reaction. The kind of the polymerization initiator is not particularly limited, and for example, a general radical polymerization initiator can be used. The radical polymerization initiator is an addition polymerization initiator which generates a radical by a heat or a reducing substance to cause a water-soluble or water-dispersible or oil-soluble persulfate or peroxide. An azobis compound or the like. Among them, a water-soluble or water-dispersible azobis compound is preferred, and 2,2'-azobis(2-methylpropenefluorene) dihydrochloride or (2,2'-azobis) can be suitably used. (2-methylpropionic acid) dimethyl) and the like.
The time for carrying out the above steps is not particularly limited, but an aqueous solution of the ethylenically unsaturated monomer b is dropped over 5 to 12 hours from the viewpoint of maintaining a large amount of monoallylamine-based monomer a, such as a large amount of hydrazine and stability. It is good, and it is especially good to drip after 6~8 hours.

The step of dropping the aqueous solution of the ethylenically unsaturated monomer b into the aqueous solution of the monoallylamine-based monomer a, the amount of the monoallylamine-based monomer a and the ethylenically unsaturated monomer b, It is not particularly limited, but the molar ratio of the monoallylamine monomer a and the ethylenically unsaturated monomer b is preferably 1:5 to 40:1, and 1:3 to 20:1 is particularly preferable, 2 : 3~20:1 is even better. By supplying the monoallylamine-based monomer a and the ethylenically unsaturated monomer b to the above molar ratio, an allylamine-based copolymer having a desired composition can be produced with excellent efficiency.
The concentration of the monoallylamine-based monomer a in the aqueous solution and the concentration of the ethylenically unsaturated monomer b in the above-described step are not particularly limited, but are not more than a certain value from the viewpoint of stable and uniform copolymerization. The concentration is preferably from a viewpoint of a polymerization efficiency or the like, and a concentration of a certain value or more is preferable. More specifically, the concentration of the monoallylamine monomer a is from 4.0 × 10 ^-3 to 6.5 ×
10 ^-3 mol/g is preferred, and 4.5 x 10 ^-3 to 6.3 x 10 ^-3 mol/g is particularly preferred. The concentration of the ethylenically unsaturated monomer b is preferably from 10 × 10 ^-3 to 20 × 10 ^-3 mol/g, particularly preferably from 10 × 10 ^-3 to 15 × 10 ^-3 mol/g.
The amount of the polymerization initiator to be used is not particularly limited, but a case where a water-soluble or water-dispersible azobis compound is used as a polymerization initiator, a monoallylamine monomer a, and an ethylenic unsaturated monomer are used. The total amount of the body b is preferably 1.0 to 10.0 mol%, and particularly preferably 2.0 to 5.0 mol%.

The excellent form of the allylamine-based copolymer obtained by the production method is also as described in the allylamine-based copolymer of the present invention. Therefore, the composition of the allylamine-based copolymer obtained by the production method, the constituent unit A derived from the monoallylamine-based monomer a, and the constituent unit B derived from the ethylenically unsaturated monomer b The molar ratio A/B is preferably 0.4 to 25, 0.4 to 15 is preferred, 0.5 to 12 is preferred, and 0.6 to 10 is particularly preferred. Regarding the excellent molecular weight, intrinsic viscosity, and the like, the allylamine-based copolymer of the present invention is also as described above.

In the method of producing an allylamine-based copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, an aqueous solution of the monoallylamine-based monomer a is used. a step of dropping an aqueous solution of the ethylenically unsaturated monomer b, a monomer composition of the feed (a molar ratio of the monoallylamine monomer a and the ethylenically unsaturated monomer b supplied to the step), And the copolymer composition (the obtained allylamine-based copolymer, the constituent unit A derived from the monoallylamine-based monomer a, and the moieties of the constituent unit B derived from the ethylenically unsaturated monomer b The difference in ratio is smaller, and the control system of the copolymer composition is easy and correct. It means that the copolymer composition can be easily and accurately controlled by the monomer composition of the feed. For example, in the obtained allylamine copolymer, the constituent unit A occupies the constituent unit A and the constituent unit. The total molar ratio A/(A+B) of B, and the monoallylamine-based monomer a supplied to the aforementioned monoalpropylamine-based monomer a in the same step as the monoallylamine-based monomer a supplied to the same step, and the aforementioned ethylene The molar ratio a/(a+b) of the total of the unsaturated monomers b is evaluated and the difference is preferably small. More specifically, the molar ratio A/(A+B) in the copolymer is preferably ±25% or less of the molar ratio a/(a+b) in the composition of the feed, and preferably ±15% or less. .

In the method for producing an allylamine-based copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, it is dripped in an aqueous solution of the monoallylamine-based monomer a. The step of the aqueous solution of the ethylenically unsaturated monomer b is carried out by copolymerizing the monomers a and b supplied to the polymerization step, whereby the allylamine-based copolymer can be produced in a high yield.
In the above production method, the yield of the feed is preferably 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.

Further, when the above production method is used, not only the yield is improved, but also a residual monomer which is not related to the copolymerization, or a single polymer in which only one monomer is polymerized, in particular, a monoallylamine having a lower reactivity is suppressed. The formation of a single polymer of the monomer a and a single polymer of the highly reactive ethylenically unsaturated monomer b.
Further, the amount of the monoallylamine-based monomer a remaining after the polymerization step is preferably 70% by weight or less, preferably 50% by weight or less, based on the amount of the monoallylamine-based monomer a supplied to the polymerization step. 40% by weight or less is particularly preferable.
Further, the amount of the individual polymer of the ethylenically unsaturated monomer b present after the polymerization step is preferably 10% by weight or less, more preferably 5% by weight or less, based on the amount of the ethylenically unsaturated monomer b supplied to the polymerization step. good. Further, the individual polymer of the ethylenically unsaturated monomer b is substantially absent, and can be obtained by a polymerization step, and the product containing the allylamine-based copolymer is in pH 2, 7, and 12. It is confirmed by water solubility or water dispersibility.

A product obtained by a process of copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, usually containing a constituent unit A derived from a monoallylamine-based monomer a, and an ethylenic property The allylamine-based copolymer constituting the unit B derived from the unsaturated monomer b further contains, without further, the un-polymerized monoallylamine-based monomer a and the ethylenically unsaturated monomer b. In particular, a monoallylamine-based monomer a having low reactivity, a single polymer polymerized by only one monomer, and a specific polymer of a highly reactive ethylenically unsaturated monomer b, etc., are used as a composition. Available for things. Here, the step of dropping the aqueous solution of the ethylenically unsaturated monomer b into the aqueous solution of the monoallylamine-based monomer a can improve the yield of the expected allylamine-based copolymer and reduce the residual sheet. Body, inhibit the formation of individual polymers.
As a result, in the composition of the product of the process, the desired allylamine-based copolymer (the constituent unit A derived from the monoallylamine-based monomer a and the ethylenically unsaturated monomer b) is reduced. The allylamine-based copolymer of the component B is a content of a component other than the component A/constituting unit B, which is a molar ratio of 0.4 to 25, and the allylamine-based copolymer. The content of the component other than the intended allylamine-based copolymer is preferably 10% by weight or less.
Further, the content of the unreacted monoallylamine-based monomer a and the 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, more preferably 10% by weight or less.

Use The allylamine-based 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, and is widely used. Water solubility in water pH, water dispersibility, water dispersibility, suitable for use in dispersants, inkjet printing chemicals, adhesives, papermaking chemicals, antistatic agents, coatings, wastewater treatment agents, anchor coating agents, synthesis Uses of a resin film, a dye fixing agent, or a molding resin.

[Examples]

Hereinafter, the present invention will be described in detail with reference to comparative examples and comparative examples, but the present invention is not limited thereto.

In the following examples/comparative examples, the physical properties/characteristics were evaluated by the following methods.

(re-sinking yield)
The yield is as defined by the following formula.

Here, the concentration of re-precipitation was measured by the following method.
Approximately 2 g of an aqueous solution of the polymer was taken, and the sample weight (A) was measured. Thereafter, the solvent was added to about 500 ml of a solvent to precipitate and precipitate a polymer. Next, the precipitate was filtered off using a glass filter. Next, the filtered solid polymer was dried in a vacuum dryer at 50 ° C for 12 hours. Finally, the weight (B) of the dried precipitate was measured. The sedimentation concentration (%) was calculated according to the following formula.

Further, the solid content concentration was measured by the following method.
Approximately 2 g of an aqueous solution of the polymer was taken, and the sample weight (C) was measured. Dry in a hot air dryer at 120 ° C for 2 hours. The weight (D) after drying was measured. The solid content concentration was calculated according to the following formula.


(feeding yield)
The amount of feed and the yield of re-precipitation were calculated according to the following formula.


(residual monomer amount)
The amount of the residual monomer detected as an impurity was measured by gas chromatography. Determination of residual monomer usage SHIMADZU GAS
CHROMATOGRAPH GC-2014, the carrier gas uses helium gas. The sample injection portion and the hydrogen ion detector (FID) were 250 ° C, the column was 110 ° C, and the linear velocity in the carrier gas was 40 cm per second, and 1 μL of the sample solution was injected at a split ratio of 1/20. The column was measured by DB-1 (manufactured by Agilent Technologies, 30 m in length, 0.32 mm in inner diameter, and 3 μm in liquid film thickness). The temperature of the column heater was maintained at 110 ° C for 5 minutes, and then the temperature was raised to 200 ° C at 10 ° C / min, and the temperature was raised to 280 ° C at 20 ° C / min, and then held for 10 minutes.

(copolymerization ratio)
By elemental analysis, the constituent unit A derived from the monoallylamine monomer a such as a copolymer or an allylamine hydrochloride, and the ethylenically unsaturated monomer b derived from methacrylic acid or the like are measured. The amount of constituent unit B is analyzed and the copolymerization ratio is analyzed.
Elemental analysis was performed in a CHN mode using a Perkin Elmer 2400II CHNS/O fully automated elemental analysis device. The carrier gas uses helium gas. The measurement system is for taking a solid sample in a tin capsule, and the combustion tube is dropped in a pure oxygen gas to burn a sample at a combustion temperature of 1800 ° C or higher, and each measurement component is detected by a chromatographic method by using a separation column and a heat conduction detector. The coefficient quantifies the content of each element.

(Intrinsic viscosity [η] of polymer)
Intrinsic viscosity [η] of polymer, in general

Expressed. η _sp is the specific viscosity and c is the volume concentration (g/dl). In the formula, [η] represents a value obtained by extrapolating c to 0. As a specific method, the polymer is dissolved in a 0.1 N NaCl aqueous solution, and as a solution having a different concentration, four kinds of solutions having a concentration of 0.25 g/dl, 0.50 g/dl, 0.75 g/dl, and 2.00 g/dl are prepared. After the solution was prepared at 30 ° C, the viscosity was measured by a Ubbelohde viscometer, and the concentration was extrapolated to 0 to determine the intrinsic viscosity [η].

(Water solubility, water dispersibility at pH 2, 7, and 12)
The allylamine-based copolymer was dissolved in water at a temperature of 25 ° C and a concentration of 0.5% by weight, and pH 2.0, 7.0, and 12.0 were prepared using a 1 N NaOH solution, and the formation of a precipitate was visually observed to determine whether or not water was soluble at each pH. Water dispersibility.

(Example 1)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 1:1
To a stirrer, a thermometer, and a 300 ml separable flask equipped with a cooling tube, 32.78 g of distilled water and 0.5 mol of allylamine hydrochloride were added. Further, in a 200 ml beaker, 100.0 g of distilled water, 0.5 mol of methacrylic acid, and a monomer (the total of allylamine hydrochloride and methacrylic acid) were mixed with 2.0 mol% of sodium hypophosphite. The internal temperature in the separable flask was warmed to 60 ° C, and 1.0 mol of the initiator V-50 (2,2'-azobis(2-methylpropionamidine) dihydrochloride) was added to the monomer. %, followed by dropwise addition of an aqueous solution of methacrylic acid through a funnel to start polymerization. The methacrylic acid was dropped over 7 hours, and 0.5 mol% of the initiator V-50 was directly added to the reaction system with respect to the monomer at intervals of 2 hours. After 24 hours, the polymerization was completed to obtain a yellow transparent highly viscous solution. The yield was confirmed by the re-sinking operation of acetone, and the yield was 100.93%. Further, the yield calculated from the amount of the monomer to be fed was 97.34%. The peaks from the methacrylic acid monomer (1700 cm ^-1 , 1155 cm ^-1 , 3000 cm ^-1 ) and the peak of the allylamine hydrochloride monomer (1155 cm ^-1 ) were confirmed by FT-IR measurement of the re-substrate. , 3000cm ^-1 ).
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility at pH 2, 7, and 12 are shown in Table 2.

(Example 2)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 3:1
Acetylamine hydrochloride 0.90 mol was prepared in a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube. Further, 60.01 g of distilled water and 0.30 mol of methacrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and the initiator V-50 (2,2'-azobis) was added relative to the monomer (the total of allylamine hydrochloride and methacrylic acid). (2-Methylpropionamidine) dihydrochloride) 1.0 mol%, and then the aqueous solution of methacrylic acid was added by dropwise addition to the microtube pump to start polymerization. The methacrylic acid was dropped over 12 hours. In the meantime, the direct addition of the initiator V-50 in the reaction system was 1 mol% after 3 hours from the start of the polymerization, and 0.5 mol% after 20 hours. After 30 hours, the polymerization reaction was completed, and a yellow transparent high viscosity solution was obtained. . The yield was confirmed by the re-sinking operation of acetone, the yield was 104.00%, and the yield calculated from the feed was 100.82%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 3)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 5:1
1.00 mol of allylamine hydrochloride was prepared in a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube. Further, 17.04 g of distilled water and 0.20 mol of methacrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and the initiator V-50 (2,2'-azobis) was added relative to the monomer (the total of allylamine hydrochloride and methacrylic acid). (2-methylpropionamidine) dihydrochloride) 0.5 mol%, and then polymerization was started by adding an aqueous methacrylic acid solution through a dropping funnel. The methacrylic acid was dropped over 12 hours. In the meantime, the direct addition of the initiator V-50 was 1.0 mol% after 4 hours from the start of the polymerization in the reaction system, and 1.0 mol% after 20 hours. After 30 hours, the polymerization reaction was terminated, and a yellow transparent highly viscous solution was obtained. The yield was confirmed by IPA re-sinking operation, the yield was 96.49%, and the yield calculated from the feed was 98.93%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility at pH 2, 7, and 12 are shown in Table 2.

(Example 4)
The ratio of allylamine hydrochloride/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b: 10:1
A propylamine hydrochloride salt of 1.20 mol was prepared in 300 ml of a separable flask containing a stirrer, a thermometer, and a cooling tube. Further, 15.39 g of distilled water and 0.12 mol of methacrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and the initiator V-50 (2,2'-azobis) was added relative to the monomer (the total of allylamine hydrochloride and methacrylic acid). (2-methylpropionamidine) dihydrochloride) 1.0 mol%, and then polymerization was started by adding an aqueous methacrylic acid solution through a dropping funnel. The methacrylic acid was dropped over 6 hours, and the initiator V-50 was directly added to the reaction system twice every 3 hours, 1.0 mol% of the monomer, and 1.5 mol% of the monomer. After 24 hours, the polymerization reaction was terminated, and a yellow transparent highly viscous solution was obtained. The yield was confirmed by IPA re-sinking operation, the yield was 100.50%, and the yield calculated from the feed was 100.02%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 5)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 15:1
1.20 mol of allylamine hydrochloride was prepared in a stirrer, a thermometer, and a 300 ml separable flask equipped with a cooling tube. Further, 10.26 g of distilled water and 0.08 mol of methacrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and the initiator V-50 (2,2'-azobis) was added relative to the monomer (the total of allylamine hydrochloride and methacrylic acid). (2-methylpropionamidine) dihydrochloride) 0.5 mol%, and then polymerization was started by adding an aqueous methacrylic acid solution through a dropping funnel. The dropwise addition of methacrylic acid was carried out over 6 hours, during which the interval was repeated every 3 hours, and 0.5 mol% of the initiator V-50 relative to the monomer was directly added to the reaction system. After 24 hours, the polymerization reaction was terminated, and a yellow transparent highly viscous solution was obtained. The yield was confirmed by IPA re-sinking operation, the yield was 98.91%, and the yield calculated from the feed was 96.57%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 6)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 20:1
1.40 mol of allylamine hydrochloride was prepared in a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube. Further, 8.98 g of distilled water and 0.07 mol of methacrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and 0.5 mg% of the monomer (the total of allylamine hydrochloride and methacrylic acid) was added to the initiator V-50 (2, 2'- Azobis(2-methylpropionamidine dihydrochloride) was added, followed by addition of an aqueous solution of methacrylic acid through a dropping funnel to initiate polymerization. The dropwise addition of methacrylic acid was carried out over 6 hours, during which the interval was repeated every 3 hours, and 1.0 mol% of the initiator V-50 relative to the monomer was directly added to the reaction system. After 24 hours, the polymerization reaction was terminated, and a yellow transparent highly viscous solution was obtained. The yield was confirmed by IPA re-sinking operation, the yield was 99.72%, and the yield calculated from the feed was 98.65%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 7)
Allylamine hydrochloride/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 2:3
21.94 g of distilled water and 0.3 mol of allylamine hydrochloride were prepared in a 300 ml separable flask equipped with a stirrer, a thermometer and a cooling tube. Further, 115.83 g of distilled water, 0.45 mol of methacrylic acid, and 4.0 mol% of sodium hypophosphite were added to a 200 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and 0.5 mg% of the monomer (the total of allylamine hydrochloride and methacrylic acid) was added to the initiator V-50 (2, 2'- Azobis(2-methylpropionamidine dihydrochloride), followed by quantification of the pump to add an aqueous solution of methacrylic acid to initiate polymerization. The methacrylic acid was dropped over 10 hours, during which time 1.0 mol% of the initiator V-50 relative to the monomer was directly added to the reaction system after 3 and 7 hours. After 30 hours, the polymerization reaction was terminated, and a yellow transparent highly viscous solution was obtained. The yield was confirmed by the re-sinking operation of acetone, the yield was 98.06%, and the yield calculated from the feed was 96.35%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 8)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 1:1
28.90 g of distilled water and 0.4 mol of allylamine hydrochloride were prepared in a 300 ml separable flask equipped with a stirrer, a thermometer and a cooling tube. Further, 60.05 g of distilled water and 0.4 mol of acrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and 1.0 mol% of the monomer (the total of allylamine hydrochloride and acrylic acid) was added to the initiator V-50 (2,2'-azo). Bis(2-methylpropionamidine) dihydrochloride) was then added to the aqueous solution of acrylic acid via a dropping funnel to initiate polymerization. The dropwise addition of acrylic acid was carried out for 7 hours, during which time 0.5 mol% of the initiator V-50 was added directly to the reaction system three times at intervals of 2 hours. After 24 hours, the polymerization reaction was terminated to obtain an orange transparent solution. The yield was confirmed by the re-sinking operation of acetone, the yield was 10.407%, and the yield calculated from the feed was 101.42%. The peaks from the acrylic monomer (1700 cm ^-1 , 1155 cm ^-1 , 3000 cm ^-1 ) and the peaks from the allylamine hydrochloride monomer (1155 cm ^-1 , 3000 cm) were confirmed by FT-IR measurement of the re-sink. ^-1 ).
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 9)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 3:1
Allylamine hydrochloride 0.6 mol was prepared in a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube. Further, 61.90 g of distilled water and 0.2 mol of acrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and 1.0 mol% of the monomer (the total of allylamine hydrochloride and acrylic acid) was added to the initiator V-50 (2,2'-azo). Bis(2-methylpropionamidine) dihydrochloride) was then added to the aqueous solution of acrylic acid via a dropping funnel to initiate polymerization. The dropwise addition of acrylic acid was carried out over 7 hours, during which time 1.0 mol% of the initiator V-50 relative to the monomer was directly added to the reaction system twice every 3 hours. After 24 hours, the polymerization reaction was terminated to obtain an orange transparent solution. The yield was confirmed by the re-sinking operation of acetone, the yield was 91.17%, and the yield calculated from the feed was 89.31%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Embodiment 10)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 5:1
1.0 mol of allylamine hydrochloride was prepared in a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube. Further, 37.17 g of distilled water and 0.2 mol of acrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and 1.0 mol% of the monomer (the total of allylamine hydrochloride and acrylic acid) was added to the initiator V-50 (2,2'-azo). Bis(2-methylpropionamidine) dihydrochloride) was then added to the aqueous solution of acrylic acid via a dropping funnel to initiate polymerization. The dropwise addition of acrylic acid was carried out over 7 hours, during which time 1.0 mol% of the initiator V-50 relative to the monomer was directly added to the reaction system twice every 3 hours. After 24 hours, the polymerization reaction was terminated to obtain an orange transparent solution. The yield was confirmed by IPA re-sinking operation, and the yield was 97.37%. The yield calculated from the feed was 95.24%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 11)
Allylamine hydrochloride/acrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 2:3
10.55 g of distilled water and 0.40 mol of allylamine hydrochloride were prepared in a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube. Further, 69.49 g of distilled water and 0.60 mol of acrylic acid were mixed in a 100 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and 0.5 mol% of the monomer (the total of allylamine hydrochloride and acrylic acid) was added to the initiator V-50 (2,2'-azo). The polymerization was started by adding bis(2-methylpropionamidine dihydrochloride) followed by quantification of the aqueous solution of acrylic acid. The dropwise addition of acrylic acid was carried out over 12 hours, during which time 1.0 mol% of the initiator V-50 relative to the monomer was directly added to the reaction system over 3 and 18 hours. After 30 hours, the polymerization reaction was terminated to obtain an orange transparent solution. The yield was confirmed by the re-sinking operation of acetone, the yield was 105.42%, and the yield calculated from the feed was 106.13%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Embodiment 12)
Allylamine decylamine sulfate/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 1:1
55.63 g of distilled water and 0.3 mol of allylamine decylamine sulfate were prepared in a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube. Further, 60.0 g of distilled water, 0.3 mol of methacrylic acid, and 2.0 mol% of sodium hypophosphite with respect to a monomer (total of allylamine guanamine sulfate and methacrylic acid) were mixed in a 200 ml beaker. The internal temperature in the separable flask was warmed to 60 ° C, and the initiator V-50 (2,2'-azobis(2-methylpropionamidine) dihydrochloride was added relative to 1.0 mol% of the monomer. Then, the polymerization was started by adding an aqueous methacrylic acid solution through a dropping funnel. The aqueous solution of methacrylic acid was dropped over 7 hours, during which time, at intervals of 3 hours, 1.0 mol% of the initiator V-50 relative to the monomer was directly added to the reaction system. After 24 hours, the polymerization reaction was terminated to obtain a highly viscous liquid of a yellow transparent solution. The yield was confirmed by the re-sinking operation of acetone, and the yield was 98.03%. Further, the yield calculated from the feed was 97.55%. The peaks from the methacrylic acid monomer (1700 cm ^-1 , 1155 cm ^-1 , 3000 cm ^-1 ) and the peaks derived from the allylamine decylamine sulfate monomer were confirmed by FT-IR measurement of the re-sinking material ( 1155cm ^-1 , 3000cm ^-1 ).
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 13)
Allylamine decylamine sulfate/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 3:1
Prepare 77.75 g of distilled water and 0.45 mol of allylamine decylamine sulfate in a 300 ml separable flask equipped with a stirrer, a thermometer and a cooling tube. In a 100 ml beaker, 19.24 g of distilled water and 0.15 mol of methacrylic acid were mixed. Monomer (total of allylamine guanamine sulfate and methacrylic acid) 1.0 mol% sodium hypophosphite. The internal temperature in the separable flask was warmed to 60 ° C, and the initiator V-50 (2,2'-azobis(2-methylpropionamidine) dihydrochloride was added relative to 1.0 mol% of the monomer. Then, the polymerization was started by adding an aqueous methacrylic acid solution through a dropping funnel. The aqueous solution of methacrylic acid was dropped over 8 hours, and the initiator V-50 was added directly to the reaction system with respect to 1.0 mol% of the monomer, twice every 3 hours. After 24 hours, the polymerization reaction was completed, and a highly viscous liquid of a yellow transparent solution was obtained. The yield was confirmed by a re-sinking operation of acetone, and the yield was 94.72%. Further, the yield calculated from the feed was 93.14%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Example 14)
Allylamine decylamine sulfate/methacrylic acid copolymer, monoallylamine monomer a: ethylenically unsaturated monomer b ratio 5:1
Into a 300 ml beaker, distilled water of 28.00 g and methacrylic acid (0.14 mol) were prepared by dissolving 49.26 g of distilled water in a separable flask equipped with a stirrer, a thermometer, and a cooling tube, and 0.4 mol of allylamine sulfonamide sulfate. The internal temperature in the separable flask was warmed to 60 ° C, and the initiator V-50 (2,2'-azobis(2-methylpropionamidine) dihydrochloride was added relative to 1.0 mol% of the monomer. Then, the polymerization was started by adding an aqueous methacrylic acid solution through a dropping funnel. The aqueous methacrylic acid solution was dropped over 8 hours, and the initiator V-50 was added directly to the reaction system with 1.0 mol% of the monomer directly at intervals of 3 hours. After 24 hours, the polymerization reaction was terminated to obtain a highly viscous liquid of a yellow transparent solution. The yield was confirmed by IPA re-sinking operation, and the yield was 96.22%. Further, the yield calculated from the feed was 98.93%.
The results are shown in Table 1.
Further, the evaluation results of water solubility and water dispersibility in pH 2, 7, and 12 are shown in Table 2.

(Comparative Example 1)
Manufacture of allylamine guanamine sulfate/acrylic acid copolymer of the prior art, ratio of monoallylamine monomer a: ethylenically unsaturated monomer b: 2:3
In a 300 ml separable flask equipped with a stirrer, a thermometer, and a cooling tube, 99.62 g of methanol, 0.3 mol of allylamine decylamine sulfate, 0.45 mol of acrylic acid, and an internal temperature of 50 ° C were prepared. After the internal temperature was stabilized, the initiator V-601 (2, 2' was added to 2.5 mol% relative to the monomer (the total of allylamine guanamine sulfate and acrylic acid) after 2.5 hours relative to the monomer. -Azobis(2-methylpropionic acid) dimethyl), and the polymerization reaction was completed after 48 hours. The white precipitate precipitated at the bottom of the flask was filtered to obtain 150.31 g of a highly viscous yellow turbid solution. The individual polymer of acrylic acid was removed by IPA re-sinking operation to obtain an allylamine guanamine sulfate/acrylic acid copolymer as a filtrate. The re-precipitation yield of the obtained copolymer was 67.08%, and the yield calculated from the feed was 50.91%. Further, it is dissolved in water and dissolved only under a specific pH condition under a high alkali.
The results are shown in Tables 1 and 2.

(Comparative Example 2)
Manufacture of allylamine guanamine sulfate/acrylic acid copolymer of the prior art, ratio of monoallylamine monomer a: ethylenically unsaturated monomer b: 2:3
28.78 g of methanol and 0.3 mol of allylamine decylamine sulfate were prepared in a 300 ml separable flask equipped with a stirrer, a thermometer and a cooling tube. Further, 75.34 g of methanol and 0.45 mol of acrylic acid were mixed in a 100 ml beaker. After the internal temperature was heated to 50 ° C, the internal temperature was stabilized, and the initiator V-601 (2,2'-azo was added with respect to 2.5 mol% of the monomer (the total of allylamine guanamine sulfate and acrylic acid). Bis(2-methylpropionic acid) dimethyl), followed by quantification of the pump, was carried out by dropping an acrylic monomer methanol solution. The dropwise addition of the acrylic monomer was carried out over 8 hours, and after 24 hours from the initiation of the polymerization, 2.5 mol% of the initiator V-601 was directly added to the reaction system with respect to the monomer, and the reaction was continued for 48 hours. After completion of the reaction, the white precipitate precipitated at the bottom of the flask was filtered to obtain 106.00 g of a highly viscous yellow turbid solution. The individual polymer of acrylic acid was removed by IPA re-sinking operation to obtain the allylamine guanamine sulfate/acrylic acid copolymer of the filtrate. The re-precipitation yield of the obtained copolymer was 68.45%, and the yield calculated from the feed was 35.08%. Moreover, it is not dissolved in water and is only dissolved in a specific pH condition under high alkali.
The results are shown in Tables 1 and 2.

[Industrial availability]

The present invention is a copolymer of a monoallylamine monomer having an expected composition and degree of polymerization and an ethylenically unsaturated monomer, which provides practical efficiency and cost, and has a practically high value to achieve significant technical effects. In the various fields of the chemical industry, the paper industry, and the electrical and electronics industry, there is a high possibility of use.

Claims (14)

An allylamine-based copolymer having a constituent unit A derived from a monoallylamine-based monomer a and an allylamine-based copolymer constituting a unit B derived from an ethylenically unsaturated monomer b, The molar ratio of the constituent unit A/constituting unit B is 0.4 to 25. The allylamine-based copolymer of claim 1, which is water-soluble or water-dispersible in pH 2, 7, and 12. The allylamine-based copolymer according to claim 1 or 2, wherein the intrinsic viscosity [η] is 0.03 (dl/g) or more. The allylamine-based copolymer according to any one of claims 1 to 3, wherein the monoallylamine-based monomer a contains monoallylamine hydrochloride, monoallylamine sulfate, monoolefin At least one monomer selected from the group consisting of propylamine phosphate and monoallylamine guanamine sulfate. The allylamine-based copolymer according to any one of claims 1 to 4, wherein the ethylenically unsaturated monomer b contains (meth)acrylic acid. A composition comprising the allylamine-based copolymer according to any one of claims 1 to 5, wherein the content of the unreacted monoallylamine-based monomer a and the ethylenically unsaturated monomer b is It is 15% by weight or less. A method for producing an allylamine-based copolymer by copolymerizing a monoallylamine-based monomer a and an ethylenically unsaturated monomer b, which has an aqueous solution of the monoallylamine-based monomer a The step of dropping an aqueous solution of the ethylenically unsaturated monomer b. In the method of claim 7, the foregoing steps are carried out in a temperature range of 0 to 100 °C. The method of claim 7 or 8, wherein the monoallylamine-based monomer a supplied to the aforementioned step and the molar ratio of the ethylenically unsaturated monomer b are 1:5 to 40:1. The method of any one of the above items 7 to 9, wherein the allylamine-based copolymer produced, the constituent unit A derived from the monoallylamine-based monomer a, and the ethylenically unsaturated single The molar ratio A/B of the constituent unit B derived from the body b is 0.4 to 25. The method according to any one of claims 7 to 10, wherein, in the allylamine-based copolymer, the constituent unit A occupies a molar ratio A/(A+B) of the total of the constituent unit A and the constituent unit B The monoallylamine-based monomer a supplied to the foregoing step occupies the total molar ratio a/ of the monoallylamine-based monomer a and the ethylenically unsaturated monomer b supplied in the same step. Within ±25% of (a+b). The method of any one of claims 7 to 11, wherein the yield of the aforementioned allylamine-based copolymer feed is 70% by weight or more. The method of any one of claims 7 to 12, wherein the amount of the monoallylamine-based monomer a remaining unpolymerized after the foregoing step is the monoallylamine-based monomer a supplied to the aforementioned step The amount is 70% by weight or less. A dispersant containing an allylamine-based copolymer according to any one of claims 1 to 5, an inkjet printing agent, an adhesive, a paper-making agent, an antistatic agent, a paint, a wastewater treatment agent, and an anchor coating film Agent, synthetic resin film, dye fixing agent, or molding resin.