JP5763899B2 - Intermediate-containing composition for water-soluble monomer and production method thereof, intermediate for water-soluble monomer, cationic group-containing monomer and production method thereof - Google Patents

Description

The present invention relates to an intermediate-containing composition for a water-soluble monomer, a method for producing the same, and a water-soluble monomer-containing composition obtained thereby. More specifically, a composition comprising an intermediate for a water-soluble monomer that can be suitably used as an intermediate for producing a compound that can be a raw material monomer for a water-soluble polymer, a method for producing the same, and It is related with the water-soluble monomer containing composition obtained by this. The present invention also relates to a cationic group-containing monomer and a method for producing the same.

A water-soluble monomer is usually used as a polymer raw material to impart water solubility or water dispersibility to a polymer. Among them, a polyalkylene glycol monomer is industrially widely used as a water-soluble monomer. For example, it is suitably used as a raw material for dispersants, detergent compositions, scale inhibitors, cement additives, thickeners and the like. Among such water-soluble monomers, a polyalkylene glycol monomer having a specific functional group as well as a polymerizable double bond has attracted attention and has been developed. A functional group is imparted to the polymer obtained in this manner, and functional addition by the functional group is being studied actively.
By the way, in the production of a water-soluble monomer having a specific functional group, a specific functional group is introduced together with a polyalkylene glycol chain that exhibits characteristics such as water solubility. First, several synthesis techniques are disclosed.

For example, a conventional method for synthesizing a polyalkylene glycol monomer having a specific functional group is a method for producing a polyalkylene glycol compound having a carboxyl group and / or a salt of a carboxyl group and having a specific structure. As one method, a method of reacting a compound obtained by adding an alkylene oxide to an unsaturated alcohol and epichlorohydrin and reacting a compound having a specific reactive group and a carboxyl group with the resulting reaction product is disclosed. (For example, refer to Patent Document 1).
Examples of the compound having the same structure as the reaction product obtained by reacting the above-described unsaturated alcohol-added compound with alkylene oxide and epichlorohydrin include one of the monomer components of the polyether copolymer. For example, a monomer having a specific structure is disclosed (for example, see Patent Documents 2, 3, and 4). In addition, a monomer having a specific structure is disclosed as a monomer component for synthesizing a specific polyether polymer having an oligooxyethylene side chain (see, for example, Patent Document 5).

On the other hand, a cationic polymer obtained by polymerizing a cationic group-containing monomer that is one of water-soluble monomers having a specific functional group has conventionally been a coagulant, a flocculant, a printing ink, Adhesives, detergent additives, soil conditioning (modifying) agents, flame retardants, shampoos, hair sprays, soaps, cosmetic additives, anion exchange resins, dye mordants and auxiliaries for fibers and photographic films, pigments in papermaking It is used in a wide range of fields such as spreading agents, paper strength enhancers, emulsifiers, preservatives, fabric and paper softeners, and lubricant additives.
For example, in US Pat. No. 6,099,089, a representative cationic monomer, a copolymer of diallyldimethylammonium chloride and a hydrophobic comonomer, is a laundry additive for preventing color flow and / or dye transfer from the fiber. It is known that it can be used as

However, with the recent increase in consumer awareness of environmental issues, the performance required for laundry additives (detergent additives) is changing. In other words, households using drum-type washing machines are increasing due to consumers' desire to save water and reduce drainage. Washing under water-saving conditions makes it more difficult than ever to transfer dye from clothing to clothing during washing, so it is required to have better performance to suppress dye transfer (prevention of dye transfer) than before. This is the current situation. Furthermore, the demand for liquid detergents, in particular concentrated liquid detergents, has increased due to their suitability for use in drum-type washing machines. In order to mix with concentrated liquid detergents, detergent additives having excellent compatibility with surfactants are also required.

JP 2010-132814 A (1-2, 15-17 pages) European Patent Publication No. 0838487 (page 1-2) Republished patent WO98 / 007772 (page 47) Republished Patent WO 97/042251 (Page 50) Japanese Unexamined Patent Publication No. Sho 63-241026 (page 1-2) International Publication No. 04/056888 Pamphlet

As described in Patent Document 1 described above, a method for producing a water-soluble polyalkylene glycol monomer has been studied. However, in order to more suitably use it as a polymerization raw material for various polymers, it is further necessary. There was room for improvement.
That is, the water-soluble monomer preferably has a polymerizable double bond at its end, and more preferably has a specific functional group at the other end. As a result, while ensuring the polymerizability of the monomer, the specific functional group is located at the end of the polymer side chain when the polymer is formed, and the characteristics derived from the specific functional group are exhibited. There is an advantage that it is easy.
Therefore, it has been studied to prepare a water-soluble monomer having such a structure, but it has a polymerizable terminal double bond and has a functional group at the other end, and a polyalkylene glycol chain. When a water-soluble polymer is produced by polymerizing a polyalkylene glycol monomer as a water-soluble monomer that exhibits water-solubility, gelation occurs and the yield of the water-soluble polymer decreases. I understood.
In order to prepare such a polyalkylene glycol monomer, an intermediate as a raw material is necessary, which affects the polymerization characteristics of the water-soluble monomer from which the intermediate is obtained. It has been found that there is a problem that causes problems during the combined manufacturing.

In addition, as described above, despite the fact that various cationic polymers have been reported in the past, the needs of new customers in recent years (for example, high ability to prevent dye migration when used as a detergent additive). Actually, it cannot be said that it can cope with (expressed polymer).

The present invention has been made in view of the above-described situation, and has a polymerizable terminal double bond, and can be suitably used for the production of a water-soluble polymer, and can produce a water-soluble polymer in a high yield. Composition comprising an intermediate for water-soluble monomer that can be suitably used for the production of a water-soluble polyalkylene glycol monomer, its production method, and a composition comprising a water-soluble monomer obtained thereby The purpose is to provide goods. Another object of the present invention is to provide a novel cationic group-containing monomer that can be used as a raw material for the cationic polymer and a method for producing the same.

The present inventors polymerize a polyalkylene glycol-based monomer as a water-soluble monomer having a polymerizable terminal double bond and having a specific functional group and exhibiting water solubility by a polyalkylene glycol chain. In the case of producing a water-soluble polymer, first, it has been found that the yield of the water-soluble polymer is lowered because gelation occurs as described above. Then, paying attention to the intermediate for synthesizing the polyalkylene glycol-based monomer, when producing the intermediate, a by-product of a specific structure having two unsaturated bonds in the structure is simultaneously generated, It was found that this by-product acts as a crosslinking component during the production of the water-soluble polymer, which is a major cause of gelation. Then, the content of the specific by-product is variously studied, and the content of the compound having the specific structure in the composition including the intermediate is within a specific range. It was found that when a water-soluble polymer is produced, the gelation reaction during the polymerization reaction can be sufficiently suppressed, and the water-soluble polymer can be produced in good yield. Is. In addition, when the content of the compound having the specific structure is within a specific range, not only can the water-soluble polymer be produced with good yield, but the produced water-soluble polymer is further adsorbed to mud and cloth. It has also been found that new functions can be imparted, such as imparting performance and making it possible to make a polymer having a low viscosity even as a high molecular weight polymer.
Thus, in the intermediate-containing composition for a water-soluble monomer, the content of the specific component is in a specific range, and the intermediate is contained in a specific amount, so that the above-mentioned problem is solved brilliantly, Further, the inventors have conceived that a new function can be imparted to a water-soluble polymer obtained from the intermediate-containing composition, and the present invention has been achieved.

In order to achieve the above object, the present inventor further examined a cationic group-containing monomer which is a raw material for various cationic polymers / copolymers. As a result, it has been found that a polymer made from a specific cationic group-containing monomer as a raw material has, for example, an excellent ability to prevent dye migration and compatibility with a surfactant when used as a detergent additive. did. Based on the above findings, the present invention has been completed.

That is, the present invention provides the following general formula (1);

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is an average added mole number of an oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300.) A body-containing composition, wherein the composition has the following general formula (2):

(In the formula, R ⁰ is the same or different and represents a hydrogen atom or a methyl group. R ¹ is the same or different and represents a methylene group, an ethylene group or a direct bond. X represents —CH ₂ —CH ( OR ² ) —CH ₂ —O— or a direct bond, R ² represents a hydrogen atom or a glycidyl group, Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. Is an average added mole number of an oxyalkylene group (—Y ¹ —O—), which is the same or different and represents a number of 1 to 300. The content of (B) is 0.1 to 6.0 mol% with respect to the content of compound (A), and the content of compound (A) is an intermediate-containing composition for water-soluble monomers. Water that is 50 to 100% by mass with respect to 100% by mass of the nonvolatile content of the product A sexual monomer-body intermediate containing composition.

The present invention also provides the following general formula (11):

(Wherein R ⁰ represents a hydrogen atom or a CH ₃ group, R ¹ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ² , R ³ and R ⁴ are the same or different. Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, and n is an average of oxyalkylene groups (—Y ¹ —O—). It represents a number of added moles, is a number of ^{1 to} 300, and X ¹ − represents a counter anion.

Another aspect of the present invention provides a method for producing a cationic group-containing monomer. The present invention relates to (i) the following general formula (12);

(Wherein R ⁰ represents a hydrogen atom or a CH ₃ group, R ¹ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and Y ¹ is the same or different and has 2 to 20 carbon atoms. N represents an average number of added moles of an oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300.) and an epihalohydrin A cationic group-containing monomer comprising: a step of reacting an alkali compound with a alkaline compound; and (ii) a step of reacting the reaction product obtained in step A with a tertiary amine salt (step B). It is also a manufacturing method.

In addition, the present invention provides (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12), an epihalohydrin, and an alkali compound (step A), and (ii) step A. A cationic group comprising a step of reacting the obtained reactant with a secondary amine (step C), and (iii) a step of reacting the reactant obtained in step C with a quaternizing agent (step D). It is also a method for producing the containing monomer.
In addition, the present invention provides (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12) and an epihalohydrin in the presence of a catalyst (step E), and (ii) step E. It is also a method for producing a cationic group-containing monomer comprising a step of reacting the obtained reaction product with a tertiary amine (step F).
The present invention also includes (i) a cationic group-containing monomer comprising a step (Step G) of reacting the polyalkylene glycol chain-containing monomer represented by the general formula (12) with a glycidyl trialkylammonium salt. It is also a body manufacturing method.
The present invention is described in detail below.

The intermediate-containing composition for a water-soluble monomer of the present invention has the following general formula (1):

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is an average addition mole number of the oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300), and the following general formula (2) ;

(In the formula, R ⁰ is the same or different and represents a hydrogen atom or a methyl group. R ¹ is the same or different and represents a methylene group, an ethylene group or a direct bond. X represents —CH ₂ —CH ( OR ² ) —CH ₂ —O— or a direct bond, R ² represents a hydrogen atom or a glycidyl group, Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. Is an average added mole number of an oxyalkylene group (—Y ¹ —O—), which is the same or different and represents a number of 1 to 300). Each of them may be one kind or two or more kinds. The intermediate-containing composition may contain other components as long as it contains the compound (A) and the compound (B).

The compound (A) is represented by the following general formula (1);

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is an average addition mole number of the oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300), and the compound is a terminal glycidyl group. Can be made into compounds having various functional groups. The compound having various functional groups can be polymerized by a polymerizable carbon-carbon double bond, has various functional groups at the end of the side chain, and has water solubility due to the side chain oxyalkylene group. The polymer shown can be obtained. In addition, for example, when the compound having various functional groups and an acrylate ester are copolymerized, a functional group derived from the acrylate ester and a compound having the various functional groups in the obtained copolymer. The functional group at the terminal end of the side chain is present at a position separated in the structure of the copolymer by the oxyalkylene group of the side chain, and the copolymer weight obtained due to the positional relationship of such a functional group It is expected that new physical properties may be added to the coalescence. Thus, the compound (A) is an intermediate for a water-soluble monomer that is a base when synthesizing a monomer used to synthesize a water-soluble polymer having various functional groups at the side chain ends. As a useful compound.
That is, the following general formula (1);

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is an average added mole number of an oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300). It is one of.
The above intermediate for water-soluble monomer is synthesized when synthesizing a monomer used to synthesize a water-soluble polymer having various functional groups at the end of the side chain. However, it is also possible to synthesize a polymer by polymerizing itself. That is, the intermediate for a water-soluble monomer can also be used as a monomer for synthesizing a polymer. Therefore, it is further possible to synthesize a polymer using the composition for the water-soluble monomer intermediate-containing composition of the present invention including the water-soluble monomer intermediate. It can also be used as a monomer-containing composition.

In the general formula (1), R ⁰ represents a hydrogen atom or a methyl group, and R ¹ represents a methylene group, an ethylene group, or a direct bond.
Here, in the present specification, R ¹ represents a direct bond in the structure represented by CH ₂ ═C (R ⁰ ) —R ¹ —O— in the general formula (1). ₂ represents a structure represented by C (R ⁰ ) —O—. That is, CH ₂ ═C (R ⁰ ) —R ¹ — means that when R ⁰ is a methyl group and R ¹ is a methylene group, a methallyl group, R ⁰ is a methyl group, and R ¹ is an ethylene group isoprenyl. Group, R ⁰ is a methyl group, R ¹ is a direct bond, an isopropenyl group, R ⁰ is a hydrogen atom, R ¹ is a methylene group, an allyl group, R ⁰ is a hydrogen atom, and R ¹ is an ethylene group Is a butenyl group, R ⁰ is a hydrogen atom, and when R ¹ is a direct bond, it means a vinyl group.
In the general formula (1), a group having a carbon-carbon double bond to be polymerized when the monomer derived from the compound (A) is polymerized, that is, CH ₂ ═C (R ⁰ ) —. R ^1- is preferably an isoprenyl group, a methallyl group, an allyl group, or a vinyl group from the viewpoint of polymerizability. More preferably, it is an isoprenyl group, a methallyl group, or an allyl group. Since the concern of gelation increases as the polymerizability increases, the effect of suppressing the gelation of the present invention is maximized. The group is particularly preferred.

In the general formula (1), Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. However, since the water solubility of the monomer derived from the compound (A) is improved, Y 1 ¹ is preferably an ethylene group, a propylene group or a butylene group, particularly preferably an ethylene group or a propylene group.
Examples of the alkylene group may be a one, may be two or more, but if it is two or more, the - oxyalkylene structure (Y 1 ^-O-) a random shape May be continuous, alternately continuous, or block-like.

In the above general formula (1), n is an average addition mole number of the oxyalkylene group ^(-Y 1 -O-), represents the number of 1 to 300, n is 2 or more. When the average addition mole number of the oxyalkylene group (—Y ¹ —O—) of the compound (A) is within such a range, the compound (A) and further a single amount derived from the compound (A) Since the body has a high boiling point, the compound (A) or the monomer derived from the compound (A) cannot be purified by distillation or the like, and is produced simultaneously with the synthesis of the compound (A). Difficult to separate from by-products. Therefore, when the number of n in the general formula (1) is large and it is difficult to purify the compound (A), the water content of the present invention in which the content of the specific component of the by-product to be generated is a specific amount. This is because the effect of the present invention that a water-soluble polymer obtained by using the intermediate-containing composition for a polymerizable monomer can be produced with high yield will be more noticeable. The n is more preferably 5 or more. Furthermore, from the viewpoint of ease of handling due to water solubility and fluidity of the monomer derived from the compound (A), n is preferably 2 or more. More preferably, it is 5 or more, More preferably, it is 10 or more. Further, n is preferably 200 or less, more preferably 150 or less, and still more preferably 100 or less, because the polymerizability of the monomer derived from the compound (A) becomes good. Especially preferably, it is 50 or less.

As will be described later, the compound (A) used in the present invention is represented by the following general formula (I);

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is the average number of added moles of the oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300.) The compound (I) represented by epihalohydrin is synthesized as a reaction raw material. As a kind of by-product during the reaction, the following general formula (2):

(In the formula, R ⁰ is the same or different and represents a hydrogen atom or a methyl group. R ¹ is the same or different and represents a methylene group, an ethylene group or a direct bond. X represents —CH ₂ —CH ( OR ² ) —CH ₂ —O— or a direct bond, R ² represents a hydrogen atom or a glycidyl group, Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. Is the average number of moles added of the oxyalkylene group (—Y ¹ —O—), which is the same or different and represents a number of 1 to 300). . The compound (B) has a structure obtained by dimerizing the compound (I) as a reaction raw material through a group represented by X in the general formula (2). Therefore, in the general formula (2), R ^{0, R 1, Y} 1, n is the same as ^{R 0,} R ^{1, Y} 1, n in the general formula (1).

In the above general formula (2), X represents —CH ₂ —CH (OR ² ) —CH ₂ —O— or a direct bond, and R ² represents a hydrogen atom or a glycidyl group, but the compound (B ) As a by-product contained in the following general formula (3), wherein X is —CH ₂ —CH (OH) —CH ₂ —O—;

^{(Wherein, R 0, R 1, Y} 1, n is the same as in the general formula (2).) And a compound represented by (B-1), X is _-CH 2 -CH ^{(OR 2')} -CH ₂ -O- (. However, ^{R 2'is} representative of a glycidyl group) following general formula is (4);

(Wherein R ⁰ , R ¹ , Y ¹ , and n are the same as those in the general formula (2)), and the following general formula (X) in which X is a direct bond ( 5);

(Wherein, R ⁰ , R ¹ , Y ¹ , and n are the same as those in General Formula (2)). When the compound (B-1) synthesizes the compound (A) from the compound (I) and epihalohydrin, the compound (I) as a reaction raw material reacts with the compound (A) as a reaction product. The compound (B-2) is a compound produced by the reaction of the compound (B-1) produced as a by-product with epihalohydrin, and the compound (B-3). Is a compound produced by dimerization of compound (I) as a reaction raw material.

In the intermediate-containing composition for a water-soluble monomer of the present invention, the content of the compound (B) is 0.1 to 6.0 mol% with respect to the content of the compound (A), and the compound Content of (A) is 50-100 mass% with respect to 100 mass% of non volatile matters of the intermediate-containing composition for water-soluble monomers. Here, the non-volatile content of the intermediate-containing composition for a water-soluble monomer represents a component that does not volatilize under conditions of 130 ° C. and 1 atm, and therefore the composition contains a solvent. In this case, a solvent such as water that volatilizes under the conditions is not included. This is a composition in which the content of the compound (B), which is a kind of by-product simultaneously generated in the synthesis step of the compound (A), in the composition sufficiently containing the compound (A) is a specific amount. Represents. In the case of obtaining a polymer by deriving and polymerizing a water-soluble monomer using the intermediate-containing composition for a water-soluble monomer of the present invention, the content of the compound (B) contained in the composition By controlling the amount to a specific amount, it is possible to sufficiently suppress the water-soluble polymer from gelling during the polymerization reaction. Further, the water-soluble polymer to be produced can be adsorbed with mud or cloth, or can be made into a polymer having a low viscosity even as a high molecular weight polymer. A new function can be imparted to the conductive polymer. This is because the composition contains an optimal amount of the compound (B) that has two unsaturated bonds in the structure and can serve as a crosslinking component during the production of the water-soluble polymer. Is assumed to be a partially crosslinked graft polymer. For example, when the water-soluble polymer thus produced is given a mud-adsorbing ability so that the water-soluble polymer is contained in a detergent composition, the polymer component is dispersed in the dispersed mud soil. It is possible to make a detergent composition capable of effectively preventing the mud from adhering to the clothes and the like and adhering again to the clothes. Thus, in the intermediate-containing composition for a water-soluble monomer, by setting the content of the compound (B) within a specific range, a highly functional water-soluble polymer can be produced in a high yield. It becomes possible. As content of a compound (B), it is preferable that it is 0.3-4.5 mol% with respect to content of a compound (A), and it is more preferable that it is 0.5-3.0 mol%. Since the effect that can impart a function to the water-soluble polymer to be produced is the highest, 0.7 to 2.5 mol% is particularly preferable.
Moreover, as content of a compound (A), if it is 50-100 mass% with respect to 100 mass% of non volatile matters of the intermediate containing composition for water soluble monomers, the intermediate for water soluble monomers It can be said that the compound (A) is sufficiently contained as the containing composition and is sufficient to induce the water-soluble monomer using the intermediate-containing composition for a water-soluble monomer of the present invention. As content of a compound (A), Preferably it is 55-95 mass%, More preferably, it is 60-90 mass%.

In the intermediate-containing composition for a water-soluble monomer of the present invention, the content of the compound (B) is the total of the compound (I) which is a reaction raw material when synthesizing the compound (A) and the compound (A). It is also one of the suitable embodiment of this invention that it is 0.1-5.0 mol% with respect to content of. That is, the compound (A) is represented by the following general formula (I):

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is an average addition mole number of the oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300), and is obtained by reacting epihalohydrin with compound (I). In the water-soluble monomer intermediate-containing composition, the content of the compound (B) is 0.1 to 5.0 mol% with respect to the total content of the compound (A) and the compound (I). In addition, the total content of the compound (A) and the compound (I) may be 50 to 100% by mass with respect to 100% by mass of the nonvolatile content of the intermediate-containing composition for a water-soluble monomer. 1 is one of the preferred embodiments of the present invention. Further, the content of the compound (B) is preferably 0.25 to 4.0 mol% with respect to the total content of the compound (A) and the compound (I), The amount is more preferably 3.0 mol%, and 0.5 to 2.0 mol% is particularly preferable because the effect that can impart a function to the produced water-soluble polymer is the highest.
The total content of the compound (A) and the compound (I) is 50 to 100% by mass with respect to 100% by mass of the non-volatile content of the intermediate-containing composition for water-soluble monomers. As the intermediate-containing composition for water-soluble monomers, the compound (A) and the compound (I) are sufficiently contained, and the water-soluble monomer is prepared using the intermediate-containing composition for water-soluble monomers of the present invention. It can be said that it is enough to guide. The total content of the compound (A) and the compound (I) is preferably 60 to 98% by mass, and more preferably 70 to 96% by mass.

Next, the manufacturing method of the intermediate containing composition for water-soluble monomers containing a compound (A) is demonstrated.
The intermediate-containing composition for a water-soluble monomer containing the compound (A) comprises a compound (I) and an epihalohydrin ½ to 1/15 (the hydroxyl group of the compound (I) (hydroxyl value conversion) / epihalohydrin). It can obtain by making it react by the molar ratio of. That is, the following general formula (1);

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is an average added mole number of an oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300.) A method for producing a body-containing composition, wherein the production method comprises the following general formula (I);

(In the formula, R ⁰ represents a hydrogen atom or a methyl group. R ¹ represents a methylene group, an ethylene group or a direct bond. Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. N is an average addition mole number of the oxyalkylene group (—Y ¹ —O—) and represents a number of 1 to 300.) The compound (I) represented by epihalohydrin is 1/2 to 1 A method for producing an intermediate-containing composition for a water-soluble monomer comprising a step of reacting at a molar ratio of / 15 (hydroxyl group of compound (I) / epihalohydrin) is also one aspect of the present invention.

Although the said reaction process can be performed by the reaction method normally used when making compound (I) and an epihalohydrin react, it is preferable to carry out by the following reaction process of (i) or (ii). (I) a step of reacting compound (I) with epihalohydrin in the presence of an alkali compound, (ii) an epihalohydrin and a Lewis acid catalyst are added to and reacted with compound (I), and then an alkali compound is added and reacted. Process. That is, it is also one of preferred embodiments of the present invention that the reaction step includes a step of reacting compound (I) with epihalohydrin in the presence of an alkali compound. Moreover, it is also one of preferred embodiments of the present invention that the reaction step includes a step of reacting compound (I) with an epihalohydrin and a Lewis acid catalyst and then reacting with an alkali compound. It is. Among the above reaction steps, a water-soluble monomer containing compound (A) is obtained by the method of reaction step (i) because side reactions such as decomposition reaction of compound (I) due to the influence of a catalyst and the like are unlikely to occur during the reaction step. It is preferable to produce an intermediate-containing composition for body.

The compound represented by the above general formula (I) in ^{(I), R 0, R 1, Y 1} , n is the same as ^{R 0, R 1, Y 1} , n in the synthesized compound (A) . As compound (I), 1 type may be used independently and 2 or more types may be used together.
In addition, the compound (I) can be produced by adding an alkylene oxide to an alkylene glycol monovinyl ether, (meth) allyl alcohol, isoprenol or an alcohol having an alkylene oxide addition structure thereof by a method usually used. it can. The produced compound (I) may be subjected to steps such as pretreatment before the above reaction step to remove the catalyst used in the production of compound (I) and the acid and alkali contained therein. It does not have to be.
The method for adding the compound (I) to the reaction system is not particularly limited, and may be added at one time before or during the reaction, or intermittently added several times before and / or during the reaction. May be.

As said epihalohydrin, following general formula (II);

(Wherein Z represents a halogen atom) is preferred, and specific examples include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Among these, epichlorohydrin is particularly preferable because it is industrially inexpensive.
These epihalohydrins may be used individually by 1 type, and may use 2 or more types together.

The amount of the compound (I) and epihalohydrin used is such that the molar ratio thereof is 1/2 to 1/15 (hydroxyl group of the compound (I) (hydroxyl value conversion) / epihalohydrin). By reacting compound (I) with epihalohydrin at a molar ratio, it is possible to suppress the formation of by-products such as compound (B) and compound (C). The amount of the compound (I) and epihalohydrin used is preferably a molar ratio of 1 / 2.5-1 / 12 (hydroxyl group / epihalohydrin of the compound (I)), more preferably 1 / 3 to 1/10, and more preferably 1/4 to 1/7.
The method for adding the epihalohydrin to the reaction system is not particularly limited, and may be added at one time before or during the reaction, or may be intermittently added several times before and / or during the reaction. .

The reaction step (i) includes a step of reacting compound (I) with epihalohydrin in the presence of an alkali compound. The reaction formula of the reaction in the reaction step (i) is shown in FIG. FIG. 1 shows that in the reaction step (i), the compound (B-1) and the compound (B-2) are produced as by-products together with the product (A).
The alkali compound is not particularly limited, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferable. These alkali compounds may be used individually by 1 type, and may use 2 or more types together.
As the amount of the alkali compound used, if too much alkali compound is present in the reaction system, the reaction proceeds more rapidly, and a large amount of by-product compound (B) is produced along with the production of compound (A). On the other hand, if there is too little alkali compound in the reaction system, the effect of adding the alkali compound may not be sufficiently obtained, so that the hydroxyl group of the compound (I) (hydroxyl value conversion) It is preferable that the molar ratio of the alkali compound is 15/1 to 1/15 (hydroxyl group / alkali compound of compound (I)). More preferably, it is 5/1 to 1/5, and more preferably 3/1 to 1/3.

The method for adding the alkali compound to the reaction system is not particularly limited, and may be added at one time before or during the reaction, or may be intermittently added several times before and / or during the reaction. Good. As a form at the time of addition, the state of aqueous solution may be sufficient, and it may be in flake form, without melt | dissolving in a solvent. However, the concentration of the alkali compound in the reaction system does not become too high at one time, and it exists throughout the reaction, so that the synthesis reaction of the compound (A) can proceed slowly. Since the amount of the crosslinking component by-produced can be controlled within a specific range, among the above-described addition methods, a method of adding a plurality of times is preferable. More preferably, it is added dropwise in the form of an aqueous solution.
In addition, when adding in the state of aqueous solution, you may react, removing water (including the water byproduced with progress of reaction) by the method used normally.

In the said reaction process (i), as usage-amount of epihalohydrin, among the above-mentioned, the molar ratio of the hydroxyl group (hydroxyl value conversion) which compound (I) has and epihalohydrin is 1 / 2.5-1 / 12 ( It is preferable that it is the hydroxyl group / epihalohydrin which compound (I) has. More preferably, it is 1/3 to 1/10, and still more preferably 1/4 to 1/7.

It is preferable to perform the said reaction process (i) using a phase transfer catalyst as needed. The phase transfer catalyst is not particularly limited, but tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride, benzyltriethylammonium chloride, benzyltriethylammonium chloride, octyltrimethylammonium chloride. Quaternary ammonium chloride such as cetyltrimethylammonium chloride; tertiary ammonium chloride such as trimethylammonium chloride and triethylammonium chloride; tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetraoctylammonium Bromide Quaternary ammonium bromides such as benzyltrimethylammonium bromide, benzyltriethylammonium bromide, octyltrimethylammonium bromide and cetyltrimethylammonium bromide; Tertiary ammonium bromide salts such as trimethylammonium bromide and triethylammonium bromide; Tetrabutylphosphonium chloride, Tetra Phosphonium salts such as butylphosphonium bromide; crown ethers such as 15-crown-5 and 18-crown-6; Among these, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide are preferable, and tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium are more preferable. A bromide, more preferably tetrabutylammonium bromide. These phase transfer catalysts may be used individually by 1 type, and may use 2 or more types together.

In the case of using the above phase transfer catalyst, the amount of the phase transfer catalyst used may be insufficient if the amount is too small. If the amount is too large, the effect corresponding to the amount used may not be obtained and the economy will not be obtained. Therefore, the molar ratio of the hydroxyl group (in terms of hydroxyl value) of the compound (I) to the phase transfer catalyst is 1 / 0.0001 to 1 / 0.3 (compound (I)). (Hydroxyl group / phase transfer catalyst). More preferably, it is 1 / 0.001 to 1 / 0.2, and still more preferably 1 / 0.005 to 1 / 0.1.

As a method for adding each reaction material in the reaction step (i), it is possible to appropriately combine the preferable addition methods for each component as described above. Among them, compound (I) and epihalohydrin are added all at once before the reaction, and an alkali compound is dropped in the form of an aqueous solution during the reaction, or intermittently in a flaky state several times during the reaction. It is suitable to carry out by the method of adding.

The reaction step (ii) includes a step of reacting compound (I) with an epihalohydrin and a Lewis acid catalyst and then adding an alkali compound to react. The reaction formula of the reaction in the reaction step (ii) is shown in FIG. In FIG. 2, Z represents a halogen atom derived from epihalohydrin. FIG. 2 shows that in the reaction step (ii), the compound (B-3) is produced as a byproduct together with the product compound (A).
The Lewis acid is not particularly limited as long as it is usually used as a Lewis acid. For example, boron trifluoride, tin tetrachloride, tin dichloride, zinc chloride, ferric chloride, aluminum chloride, tetrachloride. Examples include titanium, magnesium chloride, and antimony pentachloride. Among these, boron trifluoride, tin tetrachloride, and tin dichloride are preferable. These Lewis acid catalysts may be used individually by 1 type, and may use 2 or more types together.
If the amount of the Lewis acid catalyst used is too small, a sufficient catalytic effect may not be obtained, and if it is too large, an effect corresponding to the amount used may not be obtained, which may be economically disadvantageous. Therefore, the molar ratio of the hydroxyl group (converted to hydroxyl value) of compound (I) to the Lewis acid catalyst is 1 / 0.0001 to 1 / 0.1 (hydroxyl group of compound (I) / Lewis acid catalyst). Preferably there is. More preferably, it is 1 / 0.0005 to 1 / 0.05, and still more preferably 1 / 0.001 to 1 / 0.03.

The amount of epihalohydrin used in the reaction step (ii) is the same as the amount of epihalohydrin used in the reaction step (i). The alkali compound added in the reaction step (ii) is the same as the alkali compound in the reaction step (i).

The reaction steps (i) and (ii) are preferably carried out without using a solvent from the viewpoint of volumetric efficiency because the reaction proceeds efficiently by carrying out in the absence of a solvent. Can also be implemented. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene and toluene; ethers such as diethyl ether, tetrahydrofuran and dioxane; acetone and methyl Ketones such as methyl ketone; chlorinated hydrocarbons such as dichloromethane and dichloroethane; water; alcohols such as methanol, ethanol and isopropanol. These solvents may be used alone or in combination of two or more.

The amount of the solvent used in the case of using the solvent is not particularly limited, but is preferably 0.005 to 5 times the mass, and 0.01 to 3 times the mass of the compound (I). Is more preferable.

The reaction steps (i) and (ii) may be performed in an air atmosphere or an inert gas atmosphere. Moreover, you may carry out under any pressure under pressure reduction, atmospheric pressure, and pressurization. As reaction temperature, it is preferable that it is 0-200 degreeC, It is more preferable that it is 15-150 degreeC, It is still more preferable that it is 30-100 degreeC. From the viewpoint of the fluidity of the compound (I) which is a reaction raw material, the reaction is preferably performed at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is preferable that it is 0.1 to 50 hours, It is more preferable that it is 0.5 to 30 hours, It is still more preferable that it is 1 to 15 hours.

The reaction step includes so-called slurry reaction, and the reaction can be carried out using a reaction apparatus having a commonly used stirring apparatus. For example, using a stirred tank reactor, any of a batch reactor, a semi-batch reactor, and a continuous tank reactor can be used.

After performing the above reaction step, it is preferable to perform a derivatization reaction step of various monomers from the compound (A) after desalting, removal of excess epihalohydrin, and the like. The desalting step can be carried out by a method usually used for desalting such as sedimentation separation, centrifugation, filtration, etc., and can be carried out by appropriately setting so that the salt is sufficiently removed. In order to obtain speed, it is preferable to carry out at a temperature of 15 to 100 ° C. Further, the method for removing excess epihalohydrin is not particularly limited as long as it can be removed. For example, the epihalohydrin can be easily removed by distillation or evaporation.

Next, the water-soluble monomer containing composition induced | guided | derived using the intermediate-containing composition for water-soluble monomers of this invention is demonstrated.
The intermediate-containing composition for a water-soluble monomer of the present invention contains the compound (A) and contains compounds having various functional groups by appropriately modifying the terminal glycidyl group of the compound (A). A composition can be obtained. Since such a compound having various functional groups can be polymerized by a polymerizable terminal double bond, it has various functional groups at the end of the side chain and is water-soluble by the oxyalkylene group of the side chain. It becomes possible to obtain the polymer which shows. Therefore, the compound is useful as a water-soluble monomer.
As the compound having various functional groups, as long as it is obtained by modifying the terminal glycidyl group of the compound (A), the functional group is appropriately selected according to the physical properties to be finally added to the water-soluble polymer to be synthesized. A group can be selected and used. As a composition containing such a compound having various functional groups, for example, a water-soluble monomer obtained by reacting the water-soluble monomer intermediate-containing composition of the present invention with a functional group-containing compound. A water-soluble monomer-containing composition, wherein the water-soluble monomer is a cationic group-containing monomer obtained using a tertiary amine salt as the functional group-containing compound, A water-soluble monomer-containing composition obtained by reacting an intermediate-containing composition for a water-soluble monomer of the invention with a functional group-containing compound, wherein the water-soluble monomer contains the functional group Reaction of a water-soluble monomer-containing composition that is an amino group-containing monomer obtained by using a secondary amine as a compound, the intermediate-containing composition for a water-soluble monomer of the present invention, and a functional group-containing compound A water-soluble monomer-containing composition obtained by allowing the water-soluble monomer to A water-soluble monomer-containing composition that is a sulfonic acid group-containing monomer obtained by using a sulfite compound as the functional group-containing compound, the intermediate-containing composition for a water-soluble monomer of the present invention, and a functional group-containing composition A water-soluble monomer-containing composition obtained by reacting a compound, wherein the water-soluble monomer is an alkyl ether group-containing monomer obtained by using a hydroxyl group-containing compound as the functional group-containing compound. A certain water-soluble monomer containing composition etc. are mentioned, These water-soluble monomer containing compositions and these water-soluble monomers are also one of this invention.

When a tertiary amine salt is used as the functional group-containing compound, a cationic group-containing monomer is obtained as the water-soluble monomer-containing composition. This synthesis reaction is a reaction in which a tertiary amine salt is reacted with the glycidyl group of the compound (A), and the terminal of the compound (A) is quaternary ammonium chloride to obtain a cationic group-containing monomer. It is possible to synthesize by appropriately using a reaction method usually used for such a reaction.

When a secondary amine is used as the functional group-containing compound, an amino group-containing monomer is obtained as the water-soluble monomer-containing composition. This synthesis reaction is a reaction in which a secondary amine and a glycidyl group of the compound (A) are reacted to form a tertiary amine at the terminal of the compound (A) to obtain an amino group-containing monomer. It is possible to synthesize by appropriately using the reaction method usually used in the above.
The amino group-containing monomer has an amino group at the terminal of the amino group-containing monomer, and examples of the substituent bonded to the nitrogen atom of the amino group include an alkyl group, a hydroxyl group, Examples include groups having a functional group such as a carboxyl group.

When a sulfite compound is used as the functional group-containing compound, a sulfonic acid group-containing monomer is obtained as the water-soluble monomer-containing composition. This synthesis reaction is a reaction in which a sulfite compound and a glycidyl group of the compound (A) are reacted to sulfonate the end of the compound (A) to obtain a sulfonic acid group-containing monomer. It is possible to synthesize by appropriately using the reaction method used.

When a hydroxyl group-containing compound is used as the functional group-containing compound, an alkyl ether group-containing monomer is obtained as the water-soluble monomer-containing composition. This synthesis reaction is a reaction in which a hydroxyl group of the hydroxyl group-containing compound and a glycidyl group of the compound (A) are reacted to synthesize an alkyl ether group-containing monomer containing an alkyl ether group at the terminal, such as It is possible to synthesize by appropriately using a reaction method usually used for the reaction.
In addition to the form in which the alkyl ether group-containing monomer contains an alkyl ether group at the terminal of the alkyl ether group-containing monomer, a functional group such as a carboxyl group is bonded to a carbon atom in the alkyl ether group. The form which is carrying out is also included.

After the said water-soluble monomer containing composition is obtained, you may refine | purify as needed. The purification step can be performed by a technique that is performed as a normal purification step such as extraction or washing.

[Cationic group-containing monomer of the present invention]
As described above, a cationic group-containing monomer can be mentioned as one of water-soluble monomers having a specific functional group, and the following general formula (11);

(Wherein R ⁰ represents a hydrogen atom or a CH ₃ group, R ¹ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ² , R ³ and R ⁴ are the same or different. Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ² and R ³ may combine to form a cyclic structure, and Y ¹ may be the same or different and each represents an alkylene group having 2 to 20 carbon atoms. N represents an average number of added moles of an oxyalkylene group (—Y ¹ —O—), is a number of ^{1 to} 300, and X ¹ — represents a counter anion.) A cation having a structure represented by The sex group-containing monomer is also one aspect of the present invention.

In the above general formula (11), and when ^{R 1} is a single ^{_{bond, H 2 C = C (R}} 0) of the general formula (11) -R 1 at _{-O-, H 2 C = C (} R ⁰ ) -O-means. That ^{_{H 2 C = C (R 0}} ) -R 1 - is, ^{R 0} is CH _3, methallyl group when ^{R 1} is a CH ₂ group, ^{R 0} is CH _3, ^{R 1} is _CH 2 CH ₂ group Is an isoprenyl group, R ⁰ is a CH ₃ group, R ¹ is a single bond, an isopropenyl group, R ⁰ is a hydrogen atom, R ¹ is a CH ₂ group, an allyl group, R ⁰ is a hydrogen atom, R ^{When 1} is a CH ₂ CH ₂ group, it means a butenyl group, R ⁰ is a hydrogen atom, and when R ¹ is a single bond, it means a vinyl group.

R < ² >, R < ³ >, R < ⁴ > in the said General formula (11) is the same or different, and is a C1-C20 organic group. The organic group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group. The alkyl group, aryl group, and alkenyl group may be unsubstituted groups, or one or more of the hydrogen atoms may be substituted with other organic groups. Other substituents in this case include an alkyl group (the organic group corresponds to an unsubstituted alkyl group when the organic group is an alkyl group as a whole), an aryl group, an alkenyl group, Examples thereof include an alkoxy group, a hydroxyl group, an acyl group, an ether group, an amide group, an ester group, and a ketone group.
R ² , R ³ and R ⁴ preferably have 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 2 carbon atoms. If it exists in the said range, the cationic group containing monomer of this invention can be manufactured with a high yield.

Specific examples of R ² , R ³ and R ⁴ include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, an isobutyl group, an octyl group, a lauryl group, a stearyl group, a cyclohexyl group, and 2 An alkyl group such as ethylhexyl group; an alkenyl group such as butylene group, octylene group and nonylene group; an aryl such as phenyl group, benzyl group, phenethyl group, 2,3- or 2,4-xylyl group, mesityl group and naphthyl group A group or a group in which a part of these hydrogen atoms is substituted with an alkoxy group, a carboxyester group, an amino group, an amide group, a hydroxyl group, or the like, such as a hydroxyethyl group or a hydroxypropyl group. Since the cationic group-containing monomer of the present invention can be produced with a high yield, it is preferably a methyl group or an ethyl group.
In the general formula (11), R ² and R ³ may be bonded to form a cyclic structure. In this case, since the cyclic structure is stabilized, the ring structure is formed of N atom, R ² and R ³ . The cyclic structure to be formed is preferably a 3 to 7-membered ring, that is, the total carbon number of R ² and R ³ is 2 to 6.

In the general formula (11), Y ¹ is the same or different and is an alkylene group having 2 to 20 carbon atoms. However, since the polymerization property of the cationic group-containing monomer of the present invention is improved, Y 1 ¹ is preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an alkylene group having 2 to 3 carbon atoms. Specifically, an alkylene group having 2 to 4 carbon atoms such as an ethylene group, a propylene group, or a butylene group is preferable, and an alkylene group having 2 to 3 carbon atoms such as an ethylene group or a propylene group is particularly preferable. The alkylene group may be one type or two or more types, but in the case of two or more types, the structure of -Y ¹ -O- may be randomly continuous or alternately continuous or in a block shape It may be continuous.
In the general formula (1), that n represents an average addition mole number of the oxyalkylene group (-Y 1 ^-O-), but the number of 1 to 300, can introduce more polyalkylene glycol chains in the polymer From the viewpoint, n is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more. Further, from the viewpoint of improving the polymerizability of the cationic group-containing monomer of the present invention, n is preferably 200 or less, more preferably 150 or less, and still more preferably 120 or less.

In the cationic group-containing monomer of the present invention, a counter anion X ¹ − is present in the vicinity of the quaternized nitrogen atom. The type of the counter anion X ¹ − is not particularly limited, but is preferably a halogen atom ion or an alkyl sulfate ion. Specific examples of the halogen atom ion include a chlorine atom, bromine atom, iodine atom, and fluorine atom ion. Of these, ions of chlorine atom, bromine atom and iodine atom are preferable, and ion of chlorine atom is particularly preferable. Specific examples of the alkyl sulfate ion include methyl sulfate ion and ethyl sulfate ion. Of these, methyl sulfate ion is preferable.

The polymer obtained by polymerizing the cationic group-containing monomer of the present invention has a structure derived from the cationic group-containing monomer of the present invention. The structure derived from the cationic group-containing monomer is a structure in which the carbon-carbon double bond of the cationic group-containing monomer of the present invention is a single bond, and is represented by the following general formula (13);

(Wherein R ⁰ represents a hydrogen atom or a CH ₃ group, R ¹ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ² , R ³ and R ⁴ are the same or different. Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ² and R ³ may combine to form a cyclic structure, and Y ¹ may be the same or different and each represents an alkylene group having 2 to 20 carbon atoms. N represents the average number of added moles of the oxyalkylene group (—Y ¹ —O—), is a number from ^{1 to} 300, and X ¹ — represents a counter anion.
As the group having a carbon-carbon double bond to polymerize the cationic group-containing monomer of the present invention, that is, H ₂ C═C (R ⁰ ) —R ¹ —, an isoprenyl group, methallyl group, allyl group, vinyl Groups are preferred. From the viewpoint of polymerizability, an isoprenyl group, a methallyl group, and an allyl group are more preferable, and an isoprenyl group and a methallyl group are particularly preferable.

Next, the manufacturing method of the cationic group containing monomer of this invention is demonstrated.
[Method for Producing Cationic Group-Containing Monomer of the Present Invention]
The cationic group-containing monomer of the present invention can be produced by the above-described method, and can also be produced by a generally known production method, but the following production methods (1) to (6) It is preferable to manufacture by. According to this method, the cationic group-containing monomer of the present invention can be produced with high yield.
That is, a preferred production method (1) of the cationic group-containing monomer of the present invention comprises (i) a reaction between a polyalkylene glycol chain-containing monomer represented by the general formula (12), an epihalohydrin, and an alkali compound. A method for producing a cationic group-containing monomer comprising: a step (step A) for reacting; and (ii) a step (step B) for reacting the reaction product obtained in step A with a tertiary amine salt.

A preferred production method (2) of the cationic group-containing monomer of the present invention is the step of (i) reacting the polyalkylene glycol chain-containing monomer represented by the general formula (12), an epihalohydrin, and an alkali compound. (Step A), (ii) a step of reacting the reaction product obtained in Step A with a secondary amine (Step C), and (iii) a reaction product obtained in Step C and a quaternizing agent. It is a manufacturing method of the cationic group containing monomer including the process (process D) made to react.

A preferred production method (3) of the cationic group-containing monomer of the present invention comprises (i) a step of reacting the polyalkylene glycol chain-containing monomer represented by the general formula (12) with an epihalohydrin in the presence of a catalyst. It is a method for producing a cationic group-containing monomer, which includes (Step E) and (ii) a step (Step F) of reacting the reaction product obtained in Step E with a tertiary amine.

In the preferred production method (4) of the cationic group-containing monomer of the present invention, (i) the polyalkylene glycol chain-containing monomer represented by the general formula (12) is reacted with a glycidyl trialkyl ammonium salt. It is a manufacturing method of the cationic group containing monomer including a process (process G).

A preferred production method (5) of the cationic group-containing monomer of the present invention is a step of (i) reacting the polyalkylene glycol chain-containing monomer represented by the general formula (12) with an epihalohydrin in the presence of a catalyst. (Step E), (ii) a step of reacting the reaction product obtained in Step E with an alkali compound (Step H), and (iii) a reaction of the reaction product obtained in Step H with a tertiary amine salt. It is a manufacturing method of the cationic group containing monomer including the process (process B) to make.

A preferred production method (6) of the cationic group-containing monomer of the present invention comprises (i) a step of reacting the polyalkylene glycol chain-containing monomer represented by the general formula (12) with an epihalohydrin in the presence of a catalyst. (Step E), (ii) a step of reacting the reactant obtained in Step E with an alkali compound (Step H), and (iii) a reaction of the reactant obtained in Step H with a secondary amine. It is a manufacturing method of a cationic group containing monomer including a process (process C) and (iv) the process (process D) which makes the reaction material and quaternization agent which were obtained by process C react.

In the production method (1) to (6), in the polyalkylene glycol chain-containing monomer represented by the above general formula (12), a preferred embodiment of Y ¹ is the Y ¹ in the general formula (11) preferred embodiment It is the same.

As the polyalkylene glycol chain-containing monomer represented by the general formula (12), an alkylene oxide is usually used for an alkylene glycol monovinyl ether, (meth) allyl alcohol, isoprenol or an alcohol having an alkylene oxide addition structure thereof. What was manufactured by adding by a method can be used, and since the purity of a monomer can be made high, it is preferable.

As epihalohydrin in the production methods (1) to (3), (5) and (6), the following general formula (14);

(Wherein X ² represents a halogen atom) is preferred.
Specific examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Among these, epichlorohydrin is preferable because it is industrially inexpensive.

As the tertiary amine salt in the production methods (1) and (5), the following general formula (15);

(Wherein R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ² and R ³ may combine to form a cyclic structure. , X ^1- represents a counter ion).

In the general formula ^{(15), R 2, R} 3, R 4, X 1 - preferable ^{embodiment, R 2, R 3, R} 4, X 1 in the general formula (11) - is the same as that of the preferred embodiment .
Specific examples of tertiary amine salts include trimethylamine, dimethylethylamine, dimethylisopropylamine, dimethyl-n-propylamine, dimethylcyclohexylamine, triethylamine, triisopropylamine, tri-n-propylamine, tributylamine, and trilaurylamine. , Hydrochlorides of tertiary amines such as tristearylamine, tricyclohexylamine, tri-2-ethylhexylamine, triethanolamine, tris (2-hydroxypropyl) amine, hydrobromide, hydroiodide, nitrate, Examples include acetate, perchlorate, and paratoluenesulfonate. Among them, trimethylamine hydrochloride, triethylamine hydrochloride, and dimethylethylamine hydrochloride are preferable because the cationic group-containing monomer of the present invention can be produced with high yield.

In the production methods (2) and (6), the secondary amine is represented by the following general formula (16);

(Wherein R ² and R ³ may be the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ² and R ³ may combine to form a cyclic structure). Those represented are preferred.

In the general formula ^(16), a preferred embodiment of R 2, ^{R 3} are the same as the preferred embodiment of ^R 2, ^{R 3} in the general formula (11).
Specific examples of secondary amines include dimethylamine, methylethylamine, diethylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, dioctylamine, dilaurylamine, distearylamine, dicyclohexylamine, di- Examples include dialkylamines such as 2-ethylhexylamine; dialkanolamines such as diethanolamine and bis (2-hydroxypropyl) amine; and cyclic amines such as morpholine and pyrrole. Among them, dimethylamine, methylethylamine, diethylamine, and diethanolamine are preferred because the cationic group-containing monomer of the present invention can be produced with a high yield.

Examples of the quaternizing agent in the production methods (2) and (6) include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide; benzyl chloride, bromide Examples thereof include benzyl halides such as benzyl and benzyl iodide; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; and alkyl sulfonates such as methyl paratoluenesulfonate and ethyl paratoluenesulfonate. Of these, methyl chloride, benzyl chloride, and dimethyl sulfate are preferred because they are easily available industrially.

As a tertiary amine in the said manufacturing method (3), following General formula (17);

(Wherein R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ² and R ³ may combine to form a cyclic structure. .) Is preferred.

In the general formula ^(17), a preferred embodiment of R ^2, R 3, ^{R 4} are the same as the preferred embodiment of ^{R 2,} R 3, ^{R 4} in the general formula (11).
Specific examples of the tertiary amine include trimethylamine, dimethylethylamine, dimethylisopropylamine, dimethyl-n-propylamine, dimethylcyclohexylamine, triethylamine, triisopropylamine, tri-n-propylamine, tributylamine, trilaurylamine, Trialkylamines such as tristearylamine, tricyclohexylamine and tri-2-ethylhexylamine; and trialkanolamines such as triethanolamine and tris (2-hydroxypropyl) amine are exemplified. Among these, trimethylamine, dimethylethylamine, triethylamine, and triethanolamine are preferable because the cationic group-containing monomer of the present invention can be produced with high yield.

As a glycidyl trialkyl ammonium salt in the said manufacturing method (4), following General formula (18);

(Wherein R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ² and R ³ may combine to form a cyclic structure. , X ^3- represents a halogen atom ion).

In the general formula ^(18), a preferred embodiment of R ^2, R 3, ^{R 4} are the same as the preferred embodiment of ^{R 2,} R 3, ^{R 4} in the general formula (11).
Specific examples of the glycidyltrialkylammonium salt include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltrimethylammonium bromide, glycidyltriethylammonium bromide, and the like. Of these, glycidyltrimethylammonium chloride is preferred because it is easily available industrially.

That is, the production methods (1) to (6) are represented by the following reaction formulas.

<Reaction conditions for production method (1)>
(Reaction conditions for step A)
The method (1) for producing a cationic group-containing monomer of the present invention comprises (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12), an epihalohydrin, and an alkali compound ( Step A) is an essential step.
The reaction of Step A is performed in the presence of an alkali compound and, if necessary, a phase transfer catalyst and / or a solvent. Although it does not specifically limit as an alkali compound, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are preferable. The amount of the alkali compound used is the molar ratio of the polyalkylene glycol chain-containing monomer represented by the general formula (12) to the hydroxyl group (in terms of hydroxyl value), usually (hydroxyl group) / (alkali compound) = 15/1. Is 1/15, preferably 5/1 to 1/5, and more preferably 3/1 to 1/3. You may use an alkaline compound in the state of aqueous solution. In this case, the reaction may be performed while removing water (including water produced as a by-product with the progress of the reaction). The type of phase transfer catalyst is not particularly limited, but tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride, benzyltriethylammonium chloride, benzyltriethylammonium chloride, octyltrimethyl Ammonium chloride, cetyltrimethylammonium chloride, trimethylammonium chloride, triethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetraoctylammonium bromide, benzyltrimethylammonium bromide, benzyltri Quaternary ammonium salts such as tillammonium bromide, octyltrimethylammonium bromide, cetyltrimethylammonium bromide, trimethylammonium bromide, triethylammonium bromide; phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide; 15-crown-5, 18- And crown ethers such as crown-6. When a phase transfer catalyst is used, the amount used is usually a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (12). ) / (Phase transfer catalyst) = 1 / 0.0001 to 1 / 0.3, preferably 1 / 0.001 to 1 / 0.2, more preferably 1 / 0.005 to 1/0. .1. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained.

The amount of epihalohydrin used in the reaction of Step A is a molar ratio of the polyalkylene glycol chain-containing monomer represented by the general formula (12) to a hydroxyl group (in terms of hydroxyl value), usually (hydroxyl group) / ( Epihalohydrin) = 1/1 to 1/15, preferably 1/1 to 1/10, more preferably 1/1 to 1/5. If it is out of the range, a crosslinking component may be generated, which may cause gelation during polymerization.

The reaction in Step A is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene, and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone, Ketones such as methyl ethyl ketone; and chlorinated hydrocarbons such as dichloromethane and dichloroethane. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, Usually, it is the range of 0.005-5 times mass with respect to the polyalkylene glycol chain containing monomer represented by the said General formula (12), Preferably it is 0.00. It is the range of 01-3 times mass.
The reaction of step A may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (12), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

(Reaction conditions for step B)
In the method (1) for producing a cationic group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in step A with a tertiary amine salt (step B) is an essential step. Yes.
The reaction in Step B is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, it is the range of 0.005-5 times mass normally with respect to the reaction material obtained at the process A, Preferably it is the range of 0.01-3 times mass.

The amount of the tertiary amine salt used is usually (glycidyl group) / (tertiary amine salt) = 2/1 to the number of moles of glycidyl groups in the reaction product obtained in Step A, in a molar ratio. It is 1/2, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.3 / 1 to 1 / 1.3. The tertiary amine salt may be used in the form of an aqueous solution, but is usually an aqueous solution containing a tertiary amine salt of 30% by mass or more, preferably an aqueous solution containing 40% by mass or more, more preferably 50% by mass. % Aqueous solution. When the amount is less than 30% by mass, the selectivity of the cationic group-containing monomer obtained by the reaction may decrease.
When a catalyst is used in the above step A, the reaction may be performed as it is under the remaining catalyst. The reaction of step B may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of the fluidity of the reaction product obtained in Step A, which is a raw material, the reaction is preferably performed at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

Step A is a so-called slurry reaction and can be carried out in a reaction apparatus having a general stirring apparatus. For example, using a stirred tank reactor, any of batch, semi-batch, and continuous tank reactors can be used. After the reaction in step A, it is preferable to carry out step B after carrying out steps such as desalting and removal of excess epihalohydrin. The desalting step can be carried out by sedimentation separation, centrifugation, filtration or the like, and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed, and it is preferable to carry out at a temperature of 15 ° C. to 100 ° C. in order to obtain a sufficient separation rate. Excess epihalohydrin can be easily removed by distillation, evaporation or the like. The reaction of step B may be performed in batch or continuously, and can be performed, for example, in any apparatus of a tank type or a tube type reactor.

<Reaction conditions for production method (2)>
In the method (2) for producing a cationic group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12), an epihalohydrin, and an alkali compound ( Step A) is an essential step. Preferred conditions for step A are as described above (reaction conditions for step A).

(Reaction conditions for step C)
In the production method (2) of the cationic group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in step A with a secondary amine (step C) is an essential step.
The reaction in Step C is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, it is the range of 0.005-5 times mass normally with respect to the reaction material obtained at the process A, Preferably it is the range of 0.01-3 times mass.

The amount of secondary amine used is usually (glycidyl group) / (secondary amine) = 2/1 to 1/1 / mole ratio with respect to the number of moles of glycidyl groups in the reaction product obtained in step A. 2, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.3 / 1 to 1 / 1.3.
When a catalyst is used in the above step A, the reaction may be performed as it is under the remaining catalyst. The reaction of step C may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of the fluidity of the reaction product obtained in Step A, which is a raw material, the reaction is preferably performed at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

(Reaction conditions for step D)
In the production method (2) of the cationic group-containing monomer of the present invention, (iii) the step of reacting the reaction product obtained in step C with the quaternizing agent (step D) is an essential step.
The reaction in step D is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, it is the range of 0.005-5 times mass normally with respect to the reaction material obtained at the process A, Preferably it is the range of 0.01-3 times mass.

The amount of the quaternizing agent used in the reaction of Step D is usually (amino group) / (quaternizing agent) in a molar ratio with respect to the number of moles of amino groups of the reaction product obtained in Step C. ) = 2/1 to 1/2, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.3 / 1 to 1 / 1.3.
When a catalyst is used in the above step A, the reaction may be performed as it is under the remaining catalyst. The reaction in step D may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of the fluidity of the reactant obtained in Step C, which is a raw material, it is preferable to carry out the reaction at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.
A preferred embodiment of step A is as described above. After the reaction in Step A, it is preferable to carry out Step C after carrying out steps such as desalting and removal of excess epihalohydrin, and then to carry out Step D subsequently. The desalting step can be carried out by sedimentation separation, centrifugation, filtration or the like, and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed, and it is preferable to carry out at a temperature of 15 ° C. to 100 ° C. in order to obtain a sufficient separation rate. Excess epihalohydrin can be easily removed by distillation, evaporation or the like. The reaction in Step C may be performed in a batch or continuously, and can be performed, for example, in either a tank-type or a tube-type reactor. The reaction in the step D may be performed in a batch or continuously. For example, the reaction can be performed in any apparatus of a tank type and a tube type reactor.

The reaction product (monomer having a tertiary amino group) obtained in the above step C can be used as a raw material for a nonionic polymer or the like as it is. However, the cationic group-containing monomer of the present invention is preferably used as a raw material in order to improve the ability of the polymer to prevent dye migration.

<Reaction conditions for production method (3)>
(Reaction conditions for step E)
In the method (3) for producing a cationic group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12) and an epihalohydrin in the presence of a catalyst ( Step E) is an essential step.
The reaction in Step E may be an acid or a base as a catalyst, but an acid is preferred. The acid may be Lewis acid or Bronsted acid, but Lewis acid is preferred. As a Lewis acid, what is generally called a Lewis acid can be used. For example, boron trifluoride, tin tetrachloride, tin dichloride, zinc chloride, ferric chloride, aluminum chloride, titanium tetrachloride, magnesium chloride. And antimony pentachloride. The amount used is a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (12), usually (hydroxyl group) / (catalyst) = 1/0. 0.0001 to 1 / 0.1, preferably 1 / 0.0005 to 1 / 0.05, and more preferably 1 / 0.001 to 1 / 0.03. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained.

The amount of epihalohydrin used in the reaction of Step E is usually a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (12). ) / (Epihalohydrin) = 1/1 to 1/30, preferably 1/1 to 1/10, more preferably 1/1 to 1/5. If it is out of the range, a crosslinking component may be generated, which may cause gelation during polymerization.
The reaction in step E is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene, and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone, Ketones such as methyl ethyl ketone; and chlorinated hydrocarbons such as dichloromethane and dichloroethane. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, Usually, it is the range of 0.005-5 times mass with respect to the polyalkylene glycol chain containing monomer represented by the said General formula (12), Preferably it is 0.00. It is the range of 01-3 times mass.
The reaction of step E may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (12), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

(Reaction conditions for step F)
In the method (3) for producing a cationic group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in step E with a tertiary amine (step F) is an essential step.
The reaction in step F is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, it is the range of 0.005-5 times mass normally with respect to the reaction material obtained at the process A, Preferably it is the range of 0.01-3 times mass.

The amount of the tertiary amine used is usually (halogen group) / (tertiary amine) = 2/1 to 1/1 / molar ratio with respect to the number of moles of halogen groups in the reaction product obtained in Step E. 2, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.3 / 1 to 1 / 1.3.
When a catalyst is used in the above step E, the reaction may be performed as it is under the remaining catalyst. The reaction in step F may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of the fluidity of the reaction product obtained in step E, which is a raw material, the reaction is preferably performed at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.
The reaction of step E may be performed in a batch or continuously. For example, the reaction can be carried out in either a tank-type reactor or a tubular reactor. After the reaction in Step E, Step F may be performed after performing a step such as washing. The reaction in the step F may be performed in a batch or continuously. For example, the reaction can be performed in any apparatus of a tank type and a tube type reactor.

<Reaction conditions for production method (4)>
(Reaction conditions for process G)
In the method (4) for producing a cationic group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12) and a glycidyl trialkylammonium salt ( Step G) is an essential step.
The reaction of Step G is performed in the presence of a catalyst as necessary. Examples of the catalyst used in the reaction include alkali metal salts such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate; tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium. Chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, octyltrimethylammonium chloride, cetyltrimethylammonium chloride, trimethylammonium chloride, triethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetra Octylua Moniumuburomido, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, octyl trimethyl ammonium bromide, it can be cetyltrimethylammonium bromide, trimethylammonium bromide, etc. quaternary ammonium salts such as triethylammonium bromide exemplified. The amount used is a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (12), usually (hydroxyl group) / (catalyst) = 1/0. 0.0001 to 1 / 0.3, preferably 1 / 0.001 to 1 / 0.2, and more preferably 1 / 0.005 to 1 / 0.1. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained.

The reaction in Step G is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene, and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone, Mention may be made of ketones such as methyl ethyl ketone; and chlorinated hydrocarbons such as dichloromethane and dichloroethane. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, Usually, it is the range of 0.005-5 times mass with respect to the polyalkylene glycol chain containing monomer represented by the said General formula (2), Preferably it is 0.00. It is the range of 01-3 times mass.

The amount of the glycidyl trialkylammonium salt used in the reaction of the step G is a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (2). Usually, (hydroxyl group) / (glycidyl trialkylammonium salt) = 5/1 to 1/5, preferably 3/1 to 1/3, more preferably 1.5 / 1 to 1 / 1.5. It is.
The reaction in the step G may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (12), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.
The reaction of Step G may be performed in a batch or continuously, and for example, it can be carried out in either a tank type or a tube type reactor.

<Reaction conditions for production method (5)>
In the method (5) for producing a cationic group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12) and an epihalohydrin in the presence of a catalyst ( Step E) is an essential step. Preferred conditions for the step E are as described above (reaction conditions for the step E).

(Reaction conditions for step H)
In the method (5) for producing a cationic group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in step E with an alkali compound (step H) is an essential step.
As the alkali compound used in the reaction of the step H, the same alkali compound as used in the step A can be used. In addition, the amount used is the same as in step A.

The reaction in Step H is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, it is the range of 0.005-5 times mass normally with respect to the reaction material obtained at the process E, Preferably it is the range of 0.01-3 times mass.

(Reaction conditions for step B)
In the method (5) for producing a cationic group-containing monomer of the present invention, (iii) the step of reacting the reaction product obtained in Step H with a tertiary amine salt (Step B) is an essential step. Yes. Preferred conditions for the step B are as described above (reaction conditions for the step B).

<Reaction conditions for production method (6)>
In the method (6) for producing a cationic group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (12) and an epihalohydrin in the presence of a catalyst ( Step E) is an essential step. Preferred conditions for the step E are as described above (reaction conditions for the step E).

(Reaction conditions for step H)
In the method (6) for producing a cationic group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in Step E with an alkali compound (Step H) is an essential step. Preferred conditions for the step H are as described above (reaction conditions for the step H).

(Reaction conditions for step C)
In the method (6) for producing a cationic group-containing monomer of the present invention, (iii) a step of reacting the reaction product obtained in Step H with a secondary amine (Step C) is an essential step. Preferred conditions for step C are as described above (reaction conditions for step C).

(Reaction conditions for step D)
In the production method (6) of the cationic group-containing monomer of the present invention, (iv) the step (step D) of reacting the reaction product obtained in step C with the quaternizing agent is an essential step. . Preferable conditions for step D are as described above (reaction conditions for step D).

The cationic group-containing monomer of the present invention can be produced by the above method, but a purification step may be provided as necessary. A purification step by extraction or washing is preferable in that the amount of the crosslinking component that causes gelation during polymerization can be reduced.
Among the production methods (1) to (6), the production methods (1) to (3), (5) and (6) are preferred because the raw materials are inexpensive and simple in terms of production. Furthermore, the production method (1) is preferable because it can suppress the formation of a crosslinking component that causes gelation during polymerization, and the production method (2) is easy to select a counter anion in the cationic group-containing monomer. From the viewpoint of production, the production method (3) is preferred because less waste is produced in the reaction. Among these, the production method (1) is more preferable.

The counter anion in the cationic group-containing monomer of the present invention can be converted into a desired anion species by an ion exchange method after being obtained by the above production method, but it can be obtained by appropriately selecting the raw materials used in each production method. It is preferable to introduce the anionic species because of its simplicity. That is, in the production methods (1) and (5), the anion of the tertiary amine salt used in the step (B) is converted into a quaternizing agent in the step (D) in the production methods (2) and (6). In the production method (3), the halogen atom of the epihalohydrin in the step (E) is introduced as the counter anion in the cationic group-containing monomer with the counter anion of the glycidyl trialkylammonium salt in the step (G) in the production method (4). it can.

Next, the cationic polymer obtained by polymerizing the cationic group-containing monomer of the present invention will be described.
[Cationic polymer of the present invention]
The cationic polymer using the polymerizable monomer of the present invention as a raw material is (i) the structure (structure A) derived from the cationic group-containing monomer of the present invention represented by the general formula (13), and (Ii) It has one or more structures selected from structures derived from other cationic group-containing monomers (structure B) and structures derived from nonionic monomers (structure C).
The structure derived from the other cationic group-containing monomer of the present invention (structure B) and the structure derived from the nonionic monomer (structure C) are respectively cationic other than the cationic group-containing monomer of the present invention. A structure formed by polymerizing a group-containing monomer (other cationic group-containing monomer), a structure formed by polymerizing a nonionic monomer, and the polymerizable carbon of the monomer It is a structure in which the carbon unsaturated double bond is a single bond. For example, in the case of methyl acrylate (CH ₂ ═CHCOOCH ₃ ), which is a nonionic monomer, the structure derived from the nonionic monomer (structure C) is —CH ₂ —CH (COOCH ₃ ) —.

<Other cationic group-containing monomers>
As described above, the structure derived from the other cationic group-containing monomer that can be included in the cationic polymer of the present invention (structure B) is a cationic group-containing monomer other than the cationic group-containing monomer of the present invention. This is a structure formed by polymerization of a monomer (another cationic group-containing monomer), and the polymerizable carbon-carbon unsaturated double bond of the other cationic group-containing monomer becomes a single bond. Structure.

Other cationic group-containing monomers are preferably quaternized vinyl aromatic monomers having a heterocyclic aromatic hydrocarbon group such as vinylpyridine and vinylimidazole, dimethylaminoethyl acrylate, dimethyl Quaternization of aminoalkyl (meth) acrylates such as aminoethyl methacrylate, dimethylaminopropyl acrylate and aminoethyl methacrylate, quaternization of allylamines such as diallylamine and diallyldimethylamine, (meth) allyl glycidyl ether, isoprenyl glycidyl Quaternized products of monomers obtained by reacting tertiary amine salts with epoxy rings of ether and vinyl glycidyl ethers, quaternized products of allylamines such as diallylamine and diallyldimethylamine, (meth) allylglycidyl ether Ether, isoprenyl glycidyl ether, the epoxy ring of vinyl glycidyl ether, monomers such as quaternized monomers obtained by reacting secondary amine with a known quaternizing agent.

Preferred examples of the secondary amine include dialkylamines such as dimethylamine, diethylamine, diisopropylamine and di-n-butylamine; alkanolamines such as diethanolamine and diisopropanolamine; and cyclic amines such as morpholine and pyrrole. Known quaternizing agents include alkyl halides and dialkyl sulfuric acid.
Specific examples of the tertiary amine salt include trimethylamine hydrochloride and triethylamine hydrochloride. Examples of the salt include hydrochloride and organic acid salt.

<Nonionic monomer>
As described above, the nonionic monomer-derived structure (structure C) that can be included in the cationic polymer of the present invention is a structure formed by polymerization of a nonionic polymer, and the nonionic monomer The polymerizable carbon-carbon unsaturated double bond is a single bond.
The nonionic monomer is preferably a vinyl aromatic monomer having a heterocyclic aromatic hydrocarbon group such as vinyl pyridine or vinyl imidazole, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate. Aminoalkyl (meth) acrylates such as aminoethyl methacrylate, allylamines such as diallylamine and diallyldimethylamine, (meth) allyl glycidyl ether, isoprenyl glycidyl ether, and epoxy ring of vinyl glycidyl ether react with the secondary amine. An amino group-containing monomer such as a monomer obtained by allowing N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N- N-vinyl monomers such as tylacetamide and N-vinyloxazolidone; Amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide; 3- (meth) allyloxy-1,2 -Dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane compound added with 6 to 200 mol of ethylene oxide (3-allyloxy-1,2-di (poly) Oxyethylene ether propane, etc.), allyl ether monomers such as (meth) allyl alcohol; isoprene monomers such as isoprenol; butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate Alkyl (meth) acrylate such as Steal monomer; hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy (Metal such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc. ) Hydroxyalkyl monomers based on acrylic acid; (meth) acrylic acid alkoxy polyalkylene glycol esters, maleic acid alkoxy polyalkylene glycol esters, alkylene glycol Polyalkylene such as ether ether, vinyl ether of alkoxyalkylene glycol, (meth) allyl ether of alkylene glycol, (meth) allyl ether of alkoxyalkylene glycol, (meth) isoprenyl ether of alkylene glycol, (meth) isoprenyl ether of alkoxyalkylene glycol A glycol chain-containing monomer having 3 to 300 moles of an alcoholene glycol unit (provided that the alkoxy group has an alkoxy group at the terminal, the alkoxy group has 1 to 20 carbon atoms), styrene, indene, Examples thereof include vinyl aryl monomers such as vinyl aniline, isobutylene, and vinyl acetate.

<Composition of the cationic polymer of the present invention>
As described above, the cationic polymer of the present invention has at least one selected from (i) structure A and (ii) structures B and C as essential components. The structure A is 1 to 99% by mass and the structure B is 0 to 99% by mass with respect to 100% by mass of the structure derived from all monomers constituting the cationic polymer (structure A, structure B and structure C). The structure C preferably has a ratio of 0 to 99% by mass, the structure A is 5 to 95% by mass, the structure B is 0 to 95% by mass, and the structure C is 0 to 95% by mass. It is more preferable that the ratio is 10 to 95% by mass, the structure B is 0 to 90% by mass, and the structure C is 0 to 90% by mass.

In the present invention, when calculating the mass ratio (mass%) of the cationic group-containing monomer to the structure derived from all monomers, the counter anion is not included in the calculation, and the amino group-containing monomer When calculating the mass ratio (mass%) with respect to the structure derived from all the monomers, in the case of an amine salt, it shall calculate as a corresponding amine.

[Cationic Polymer Composition of the Present Invention]
The cationic polymer composition of the present invention contains the cationic polymer of the present invention as an essential component, and may contain only the cationic polymer. 1 or more chosen from the by-product at the time of superposition | polymerization and a water | moisture content is contained. The form of a preferable cationic polymer composition is a form containing 40-60 mass% of a cationic polymer and 40-60 mass% of water.

Next, the manufacturing method of the cationic polymer obtained by superposing | polymerizing the cationic group containing monomer of this invention is demonstrated.
[Method for Producing Cationic Polymer of the Present Invention]
As the method for producing the cationic polymer of the present invention, a known polymerization method can be used in the same manner or modified unless otherwise specified. The method for producing the cationic polymer of the present invention includes (i) a cationic group-containing monomer (also referred to as monomer a), and (ii) other cationic group-containing monomers (single amount). It can manufacture by copolymerizing the monomer component which contains 1 or more types chosen from the body b) and a nonionic monomer (monomer c) as an essential component.
Specific polymerization methods include, for example, an oil-in-water emulsion polymerization method, a water-in-oil emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a solution polymerization method, an aqueous solution polymerization method, a bulk polymerization method, and the like. Can be adopted. Among the polymerization methods exemplified above, it is preferable to employ an aqueous solution polymerization method or an emulsion polymerization method because it is highly safe and can reduce production costs (polymerization costs).

In such a production method, the monomer component may be copolymerized using a polymerization initiator. In addition, the kind and usage-amount of the monomer contained in a monomer component are set suitably so that the structural unit which comprises a cationic polymer may become as mentioned above. That is, the composition ratio of each monomer used for the polymerization of the cationic polymer is such that monomer a is 1 or more and 99 with respect to 100% by mass of all monomers (monomer a, b, c). It is preferable that the ratio is from 0 to 99% by mass, the monomer b is from 0 to 99% by mass, and the monomer a is from 5 to 95% by mass. It is more preferable that the body b has a ratio of 0 to 95% by mass and the monomer c has a ratio of 0 to 95% by mass, the monomer a is 10 to 95% by mass, and the monomer b is 0 or more. It is particularly preferable that the ratio is 90% by mass or less and the monomer c is in the range of 0 to 90% by mass.

<Polymerization initiator>
As the initiator, known ones can be used, for example, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; 2,2′-azobis (2-amidinopropane) Azo compounds such as hydrochloride, 4,4′-azobis-4-cyanoparerenic acid, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide Organic peroxides such as lauroyl peroxide, peracetic acid, di-t-butyl peroxide and cumene hydroperoxide are preferred. Of these polymerization initiators, hydrogen peroxide, persulfate, and 2,2′-azobis (2-amidinopropane) hydrochloride are preferred, and persulfate and 2,2′-azobis (2-amidinopropane) hydrochloric acid. Most preferred are salts. These polymerization initiators may be used alone or in the form of a mixture of two or more. For example, a combination of hydrogen peroxide and persulfate is a preferred form.

<Chain transfer agent>
In the method for producing the cationic polymer of the present invention, a chain transfer agent may be used as a molecular weight regulator of the polymer as long as it does not adversely affect the polymerization. Specific examples of the chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2- Thiol chain transfer agents such as mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, butylthioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; Secondary alcohol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite, and salts thereof ( Sodium bisulfite, potassium bisulfite , Sodium dithionite, potassium dithionite, sodium metabisulfite, metabisulfite potassium, etc.) and the like, and the like lower oxides and salts thereof. The chain transfer agent may be used alone or in the form of a mixture of two or more. When a chain transfer agent is used, there is an advantage that a cationic polymer to be produced can be prevented from becoming unnecessarily high in molecular weight, and a low molecular weight cationic polymer can be produced efficiently.
In the production method of the present invention, as described above, it is preferable to use sulfite and / or sulfite (hereinafter simply referred to as “sulfur (salt)”) as a chain transfer agent. In addition to sulfurous acid (salt), an initiator is used. Further, heavy metal ions may be used in combination as a reaction accelerator.

The sulfurous acid (salt) refers to sulfurous acid or hydrogen sulfite or a salt thereof, and a form in which sulfurous acid / bisulfite is a salt is preferable. When sulfite / bisulfite is a salt, in addition to the examples described above, salts of metal atoms, ammonium or organic ammonium are preferred. Examples of the metal atom include monovalent metal atoms of alkali metals such as lithium, sodium and potassium; divalent metal atoms of alkaline earth metals such as calcium and magnesium; trivalent metal atoms such as aluminum and iron And the like are preferred. As the organic ammonium (organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, it may be ammonium. Therefore, examples of the sulfite preferably used in the present invention include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite and the like, and sodium bisulfite is particularly suitable. The sulfurous acid (salt) may be used alone or in the form of a mixture of two or more.

<Reaction accelerator>
In the method for producing a cationic polymer of the present invention, a reaction accelerator may be added for the purpose of reducing the amount of an initiator used. Examples of the reaction accelerator include heavy metal ions. In the present invention, heavy metal ion means a metal having a specific gravity of 4 g / cm ³ or more. As said metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable. The ionic valence of the heavy metal ions is not particularly limited. For example, when iron is used as the heavy metal, the iron ions in the initiator may be Fe ²⁺ or Fe ³⁺ , and these may be combined. May be.
The heavy metal ions are not particularly limited as long as they are included in the form of ions. However, it is preferable to use a method using a solution in which a heavy metal compound is dissolved because the handleability is excellent. The heavy metal compound used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used. When iron is used as the heavy metal ion, the mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal compound or the like.
Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. In the case of using these heavy metal compounds, since they are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability. The solvent of the solution obtained by dissolving the heavy metal compound is not limited to water, and does not interfere with the polymerization reaction in the production of the cationic polymer of the present invention, and dissolves the heavy metal compound. Anything to do.

The method for adding the heavy metal ions is not particularly limited, but it is preferably added before the completion of the dropwise addition of the monomer, and it is particularly preferable to initially charge the entire amount. Further, the amount used is preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 50 ppm or less, and particularly preferably 30 ppm or less with respect to the total amount of the reaction solution. If it exceeds 100 ppm, the added effect is no longer seen, and the resulting copolymer is highly colored, which may be unusable when used as a detergent composition.

The content of the heavy metal ions is preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. If the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, when the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting copolymer may be deteriorated. Moreover, when there is much content of heavy metal ion, when using the polymer which is a product as a detergent builder, it may become a cause of coloring stain | pollution | contamination.

The time when the polymerization reaction is completed means the time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is neutralized with an acid component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.

In the method for producing the cationic polymer of the present invention, in the polymerization, a decomposition catalyst for the polymerization initiator or a reducing compound may be added to the reaction system in addition to the above-described compounds. Examples of the decomposition catalyst for the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Metal salts of inorganic acids; Carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid, benzoic acid, their esters and their metal salts; heterocyclic amines such as pyridine, indole, imidazole, carbazole and their derivatives Can be mentioned. These decomposition catalysts may be used alone or in combination of two or more.

Examples of the reducing compound include organic metal compounds such as ferrocene; iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, manganese naphthenate, and the like, such as iron, copper, nickel, cobalt, manganese Inorganic compounds capable of generating metal ions; boron trifluoride ether adducts, potassium permanganate, perchloric acid and other inorganic compounds; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, Sulfur-containing compounds such as benzenesulfinic acid and its substitutes, homologues of cyclic sulfinic acid such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α -Sodium thiopropionate sulfopropyl es Tercap, mercapto compounds such as α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes such as ascorbic acid and the like. These reducing compounds may also be used alone or in combination of two or more. A reducing compound such as a mercapto compound may be added as a chain transfer agent.

The combination of the chain transfer agent, the initiator, and the reaction accelerator is not particularly limited, and can be appropriately selected from the above examples. For example, combinations of chain transfer agent, initiator and reaction accelerator include sodium bisulfite / hydrogen peroxide, sodium bisulfite / sodium persulfate, sodium bisulfite / Fe, sodium bisulfite / hydrogen peroxide / Fe, sulfurous acid. Forms such as sodium hydrogensulfate / sodium persulfate / Fe, sodium hydrogensulfite / sodium persulfate / hydrogen peroxide, sodium hydrogensulfite / oxygen / Fe are preferred. More preferred are sodium persulfate / hydrogen peroxide, sodium persulfate / hydrogen peroxide / Fe, sodium bisulfite / sodium persulfate, sodium bisulfite / sodium persulfate / Fe, and most preferred sodium bisulfite / peroxide. Sodium sulfate / Fe, sodium persulfate / hydrogen peroxide / Fe.

<Amount of polymerization initiator used>
The amount of the initiator used is not particularly limited as long as it is an amount capable of initiating the copolymerization of the monomer. Preferably it is 1-12g.

When hydrogen peroxide is used as an initiator, the amount of hydrogen peroxide added is preferably 1.0 to 10.0 g, and 2.0 to 8.0 g, per mole of monomer. It is more preferable. When the amount of hydrogen peroxide added is less than 1.0 g, the polymerization average molecular weight of the resulting copolymer tends to increase. On the other hand, when the added amount exceeds 10.0 g, the effect of hydrogen peroxide cannot be obtained as the added amount increases, and the remaining hydrogen peroxide amount increases.

When using a persulfate as an initiator, the amount of persulfate added is preferably 1.0 to 5.0 g, and 2.0 to 4.0 g, per mole of monomer. It is more preferable. If the amount of persulfate added is too small, the molecular weight of the resulting copolymer tends to increase. On the other hand, if the addition amount is too large, the effect of persulfate cannot be obtained as the addition amount increases, and further, the purity of the copolymer obtained is adversely affected.

When hydrogen peroxide and persulfate are used together as an initiator, the addition ratio of hydrogen peroxide and persulfate is such that when the weight of hydrogen peroxide is 1 by weight, the weight of persulfate is 0.00. It is preferably 1 to 5.0, and more preferably 0.2 to 2.0. When the weight ratio of persulfate is less than 0.1, the weight average molecular weight of the resulting copolymer tends to be high. On the other hand, if the weight ratio of persulfate exceeds 5.0, the persulfate is wasted in the polymerization reaction system in a state where the effect of lowering the molecular weight due to the addition of persulfate cannot be obtained as much as the addition. It will be.

As a method for adding hydrogen peroxide, the amount of dripping substantially continuously with respect to the total amount used is preferably 85% by weight or more of the required predetermined amount, particularly preferably 90% by weight or more. Most preferably, is dropped. Hydrogen peroxide is continuously dropped, but the dropping speed may be changed.

The dropwise addition of hydrogen peroxide is preferably started with a delay after the start of dropping of the monomer (excluding the monomer to be initially charged) under the conditions of the polymerization temperature and pH at the time of polymerization described later. Preferably, after 1 minute or more has elapsed after the start of the dropwise addition of the cationic group-containing monomer, more preferably after 3 minutes or more, more preferably after 5 minutes or more, and most preferably after 10 minutes or more has elapsed, Is to start. By delaying the dropping start time of hydrogen peroxide, it is possible to smooth the initial polymerization start and narrow the molecular weight distribution.
The time for delaying the hydrogen peroxide dropping start time is preferably within 60 minutes, more preferably within 30 minutes after the start of dropping of the monomer.
It is possible to start the dropping of hydrogen peroxide at the same time as the dropping of the monomer, and to charge hydrogen peroxide in advance before the dropping of the monomer. It is preferably 10% or less, more preferably 7% or less, still more preferably 5% or less, and particularly preferably 3% or less.
If hydrogen peroxide exceeding 10% of the required predetermined amount is added by the time when the dropping of the monomer is started, for example, in the case of using persulfate together, the ratio of the concentration of hydrogen peroxide to persulfate increases, and polymerization is performed. May stop. On the other hand, if it starts later than 60 minutes from the start of dropping of the monomer, the chain transfer reaction due to hydrogen peroxide does not occur, so the molecular weight at the initial stage of polymerization increases.

The hydrogen peroxide dropping end time is preferably completed simultaneously with the monomer dropping end time under the conditions of the polymerization temperature and pH at the time of polymerization described later, and is 10 minutes or more earlier than the monomer dropping end time. It is more preferable to end, and it is particularly preferable to end 30 minutes or more early. In addition, even if it complete | finishes later than the dripping completion time of a monomer, it does not have a bad influence in a polymerization system especially. However, since the added hydrogen peroxide is not completely decomposed by the end of the polymerization, the effect as hydrogen peroxide is not obtained and is wasted, and a large amount of hydrogen peroxide may remain. This is not preferable because it may adversely affect the thermal stability of the obtained polymer.

In addition, the persulfate addition method is not particularly limited in view of its decomposability and the like, but the amount dripped substantially continuously with respect to the total use amount is 50% by weight or more of the required predetermined amount. It is particularly preferable that the content is 80% by weight or more, and it is most preferable to add the whole amount dropwise. The persulfate is dripped continuously, but the dripping speed may be changed.

Although there is no particular limitation on the dropping time, in the case of an initiator that decomposes relatively quickly, such as persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate under the conditions of polymerization temperature and pH at the time of polymerization described later. It is preferable to drop until the monomer dropping end time, more preferably within 30 minutes after the monomer dropping ends, and particularly within 5 to 20 minutes after the monomer dropping. preferable. Thereby, the effect which can reduce the residual amount of the monomer in a copolymer remarkably can be found. It should be noted that, even if the addition of these initiators is completed before the completion of the monomer addition, it does not particularly adversely affect the polymerization, and is set according to the residual amount of monomer in the obtained copolymer. It is good.

For these initiators that are relatively quick to decompose, the preferred range is described only for the dropping end time, but the dropping start time is not limited at all and may be set as appropriate. For example, in some cases, the dropping of the initiator may be started before the start of dropping of the monomer, or in the case of a combined system in particular, the dropping of one initiator is started and a certain time has elapsed. Then, or after completion, another initiator may be dropped. Any of these may be set as appropriate according to the decomposition rate of the initiator and the reactivity of the monomer.

The concentration of the radical polymerization initiator at the time of addition is not particularly limited, but is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. If the concentration of the initiator is less than 5% by weight, the monomer concentration during the polymerization will be very low as a result. The remaining amount of the body becomes very large. Further, the efficiency and productivity of transportation and the like are lowered, which is not preferable from the economical aspect. On the other hand, if it exceeds 60% by weight, there is a problem in terms of safety and ease of dripping.
In the method of the present invention, the addition amount of the chain transfer agent is not limited as long as the monomers a, b, and c are polymerized satisfactorily, but the total amount of monomers a, b, and c is preferable. It is 1-20g with respect to 1 mol of body components, More preferably, it is 2-15g. If it is less than 1 g, the molecular weight may not be controlled. On the other hand, if it exceeds 20 g, a large amount of impurities may be generated and the polymer content may be reduced. Especially when sulfite is used. Excess sulfite may be decomposed in the reaction system to generate sulfurous acid gas. Moreover, there is a risk of being disadvantageous economically.
As a combination of the initiator and the chain transfer agent, it is most preferable to use one or more persulfates and sulfites. In this case, the mixing ratio of persulfate and sulfite is not particularly limited, but it is preferable to use 0.5 to 5 parts by mass of sulfite with respect to 1 part by mass of persulfate. More preferably, with respect to 1 part by mass of persulfate, the lower limit of sulfite is 1 part by mass, and most preferably 2 parts by mass. Further, the upper limit of the sulfite is more preferably 4 parts by mass, and most preferably 3 parts by mass with respect to 1 part by mass of the persulfate. Here, if the amount of sulfite is less than 0.5 parts by mass, the total amount of initiator may increase when the molecular weight is lowered. Conversely, if the amount exceeds 5 parts by mass, side reactions increase and impurities due thereto. May increase.
The total amount of the chain transfer agent, initiator, and reaction accelerator used is the cationic group-containing monomer (monomer a) of the present invention, and other cationic group-containing monomers (monomer b). It is preferable that it is 2-20g with respect to 1 mol of all the monomer components which consist of a nonionic monomer (monomer c). By setting it as such a range, the cationic polymer of this invention can be produced efficiently, and the molecular weight distribution of a cationic polymer can be made into a desired thing. More preferably, it is 4-18g, More preferably, it is 6-15g.
As a method for adding the polymerization initiator and the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. In addition, the chain transfer agent may be introduced alone into the reaction vessel, or may be previously confused with each monomer a, b, c, solvent, etc. constituting the monomer component.

<Polymerization solvent>
In the present invention, the copolymerization of the monomers a, b and c is preferably carried out using a solvent capable of dissolving the monomers a and b or c, and water is added to 50% by mass or more of the solvent used. Is preferably used. Depending on the application, the mixing of the organic solvent may be severely restricted, but by using water in 50% by mass or more of the solvent used, the amount of the organic solvent used for the polymerization can be suppressed, so that after the completion of the polymerization There is an advantage that the organic solvent can be easily distilled off.
Examples of the solvent that can be used by mixing with water include lower alcohols such as methanol, ethanol and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone and diethyl ketone; ethers such as dimethyl ether and dioxane; amides such as dimethylformaldehyde. Kind. These solvents may be used alone or may be tried in the form of a mixture of two or more. From the above viewpoint, the amount of water is preferably 80% by mass or more, and most preferably water alone (ie, 100% by mass) with respect to the total amount of the solvent used. In the case of adding the organic solvent, from the viewpoint of the solubility of the monomer component and the resulting copolymer, one or more selected from the group consisting of water and a lower alcohol having 1 to 4 carbon atoms. It is preferable to use a solvent.
The amount of the solvent such as water used is preferably 40 to 200% by mass with respect to 100% by mass of the monomer component. More preferably, it is 45 mass% or more, More preferably, it is 50 mass% or more. Moreover, More preferably, it is 180 mass% or less, More preferably, it is 150 mass% or less. If the amount of the solvent used is less than 40% by mass, the resulting copolymer may have a high molecular weight. If it exceeds 200% by mass, the concentration of the obtained copolymer will be low, and solvent removal will be required. There is a fear. The solvent may be partially or wholly charged in the reaction vessel at the beginning of the polymerization, but a part of the solvent may be added (dropped) into the reaction system during the polymerization reaction, or the monomer. Components, initiators, and the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form in which they are dissolved in advance.
In the above polymerization method, as a method for adding the monomer component and the polymerization initiator to the reaction vessel, all the monomer components are charged into the reaction vessel, and copolymerization is performed by adding the polymerization initiator into the reaction vessel. By charging a part of the monomer component into the reaction vessel and adding the polymerization initiator and the remaining monomer component continuously or stepwise (preferably continuously) into the reaction vessel. A method of copolymerization; a method in which a polymerization solvent is charged in a reaction vessel and a total amount of monomer components and a polymerization initiator is added; a part of one of monomers a, b, and c is added to the reaction vessel A method in which polymerization is performed by charging, adding a polymerization initiator and the remaining monomer components into the reaction vessel (preferably continuously) is preferable. Among such methods, the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), and the dispersibility when used as a dispersant can be improved. It is preferable to carry out the copolymerization by a method in which the monomer component is successively dropped into the reaction vessel.
The polymerization method can be carried out either batchwise or continuously.
In the above polymerization method, the polymerization conditions such as the polymerization temperature are appropriately determined depending on the polymerization method used, the solvent, and the polymerization initiator. The polymerization temperature is usually preferably 0 ° C. or higher, and 150 ° C. The following is preferable. More preferably, it is 40 degreeC or more, More preferably, it is 60 degreeC or more, Most preferably, it is 80 degreeC or more. Moreover, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less. In particular, when using sulfurous acid (salt), the polymerization temperature is usually 60 ° C to 95 ° C, preferably 70 ° C to 95 ° C, and more preferably 80 ° C to 95 ° C. At this time, if the temperature is lower than 60 ° C., a large amount of impurities derived from sulfurous acid (salt) may be generated. Conversely, if it exceeds 95 ° C, toxic sulfurous acid gas may be released.
The polymerization temperature does not necessarily need to be kept almost constant in the polymerization reaction. For example, the polymerization is started from room temperature, the temperature is raised to a set temperature with an appropriate temperature increase time or rate, and then the set temperature is increased. You may make it hold | maintain, and according to the dropping method of a monomer component, an initiator, etc., you may carry out temperature fluctuation (temperature rise or temperature fall) with time during a polymerization reaction.

<Polymerization time, polymerization pressure, polymerization pH>
The polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 300 minutes. In the present invention, “polymerization time” represents the time during which a monomer is added unless otherwise specified.
The pressure in the reaction system in the polymerization method may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but in terms of the molecular weight of the resulting copolymer, The reaction system is preferably sealed and the reaction is carried out under pressure. Moreover, it is preferable to carry out under a normal pressure (atmospheric pressure) at the point of equipment, such as a pressurization apparatus, a pressure reduction apparatus, a pressure-resistant reaction container, and piping. The atmosphere in the reaction system may be an air atmosphere, but is preferably an inert atmosphere. For example, the inside of the system is preferably replaced with an inert gas such as nitrogen before the start of polymerization.
The pH during the polymerization in the polymerization is not particularly limited. When copolymerizing a vinyl carboxylate monomer such as vinyl acetate and a vinyl lactam monomer such as N-vinylpyrrolidone, the polymerization is preferably carried out under neutral conditions. When using a perbisulfite as the chain transfer agent, it is preferably carried out under acidic conditions.

[Uses of copolymer and polymer composition]
The cationic group-containing polymer (or polymer composition) of the present invention comprises a coagulant, a flocculant, a printing ink, an adhesive, a soil conditioner (modifier), a flame retardant, a skin care agent, a hair care agent, a shampoo and hair. Additives for sprays, soaps and cosmetics, anion exchange resins, dye mordants and auxiliaries for fibers and photographic films, pigment spreading agents for papermaking, paper strength enhancers, emulsifiers, preservatives, fabric and paper softeners, lubrication It can be used as an oil additive, water treatment agent, fiber treatment agent, dispersant, detergent additive, scale inhibitor (scale inhibitor), metal ion sealant, thickener, various binders, emulsifier, and the like. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, residential, hair, body, toothpaste, and automobile.

The intermediate-containing composition for a water-soluble monomer according to the present invention has the above-described configuration, whereby a water-soluble polymer can be produced with high yield, and mud or cloth is further added to the produced water-soluble polymer. Can be imparted to the water-soluble polymer, so that it can be suitably used for the production of a polyalkylene glycol monomer having a polymerizable terminal double bond that is suitably used for the production of a water-soluble polymer and exhibiting water solubility. be able to.
Further, the cationic group-containing monomer of the present invention has the above-described configuration, and has excellent copolymerizability with various nonionic monomers and other cationic monomers. And the polymer obtained from the cationic group-containing monomer of the present invention is excellent in dye transfer when used as a detergent additive, for example, due to the structure derived from the cationic group-containing monomer of the present invention. Inhibiting ability and compatibility with surfactants.

FIG. 1 is a reaction formula showing an outline of the reaction in the reaction step (i). FIG. 2 is a reaction formula showing an outline of the reaction in the reaction step (ii). 3 is a ¹ H-NMR chart of the intermediate product [A] of the monomer (1) obtained in Example 4. FIG. FIG. 4 is a ¹ H-NMR chart of the monomer (1) obtained in Example 4.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

In the following Examples and Comparative Examples, analysis and evaluation were performed as follows.
<Quantification of intermediate composition>
The quantitative determination of the isoprenol ethylene oxide average 10-mole adduct (IPN10) and the terminal glycidylated product of IPN10 (IPEG10) in the intermediate-containing composition for water-soluble monomers was performed by high performance liquid chromatography under the following conditions. The cationic group-containing monomer (IPEC10) was quantified from its conversion rate by quantifying the corresponding terminal glycidylated product of IPN10 (IPE10).
Measuring device: Hitachi High-Technologies Corporation column: Shiseido Co., Ltd. CAPCELLPAK C18 MGII (inner diameter: 4.6 mm × length: 250 mm, particle diameter: 5 μm)
Eluent: 0.1% by mass formic acid / acetonitrile = 6/4 (volume ratio)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI, UV (210 nm)
Calibration curve: It was prepared using an ethylene oxide average 10-mole adduct (IPN10) of isoprenol which is a reaction raw material alcohol. However, the amount was calculated assuming that the detection intensity of IPEG10 was the same as that of IPN10.

<Quantification of by-products>
By-products in the intermediate-containing composition for water-soluble monomers were quantified by high performance liquid chromatography under the following conditions.
Measuring device: 2695 manufactured by Waters
Column: CAPCELLPAK C18 MGII manufactured by Shiseido Co., Ltd. (inner diameter: 1.5 mm × length: 150 mm, particle diameter: 5 μm)
Eluent: 0.1% by mass formic acid / acetonitrile = 6/4
Flow rate: 0.2 mL / min
Column temperature: 30 ° C
UV detector: 210 nm
Calibration curve: It was prepared using an ethylene oxide average 10-mole adduct (IPN10) of isoprenol, which is a reaction raw material alcohol, and the amount was calculated assuming that the detection intensity of by-products was twice that of IPN10.

<Polymerization test>
An intermediate-containing composition containing IPN10 terminal glycidylated product (IPEG10) is reacted with trimethylamine hydrochloride to synthesize a water-soluble monomer-containing composition containing the corresponding cationic group-containing monomer (IPEC10). Then, a polymerization test was conducted. In the polymerization test, IPEC10 and hydroxyethyl acrylate were charged at a composition ratio of 1/2 in terms of molar ratio, and then static polymerization was performed. As a reaction initiator, sodium persulfate was used for polymerization at a reaction temperature of 80 ° C., and the resultant polymer was subjected to an adsorption ability test on mud.

<Adsorption ability test to mud>
A 0.3% polymer-containing aqueous solution in terms of solid content was prepared. (The solid content was dried by leaving the polymer aqueous solution obtained in the above polymerization test in an oven heated to 130 ° C. for 1 hour, and the solid content (%) and volatile component (%) were determined from the weight change before and after drying. 11) JIS Z 8901 powder 1 for testing (Kanto loam) was charged to 5% in a polymer-containing aqueous solution, stirred at room temperature for 20 minutes, and the clay was filtered using a filter. Absorbance at 210 nm was measured using an ultraviolet-visible spectrophotometer (measurement apparatus: UV-1650PC manufactured by SHIMADZU). As a blank, the same test was performed using pure water instead of the polymer-containing aqueous solution. From the above measurement results, the adsorption capacity to mud was determined by the following formula.
Adsorption capacity to mud (%) = [(absorbance of polymer-containing aqueous solution after test−absorbance of blank) / absorbance of polymer-containing aqueous solution before test] × 100
It was also confirmed in advance that the polymer concentration in the aqueous solution and the absorbance were in a proportional relationship at a measurement wavelength of 210 nm.

Example 1
In a 1 L four-necked flask equipped with a stirring blade, a thermometer, and a cooling tube, the following chemical formula (6):

The total amount of isoprenol ethylene oxide 10 mol adduct (IPN10, hydroxyl value: 106.5 mgKOH / g) 200.2 g and epichlorohydrin (ECH) 351.6 g are charged all at once, and the internal temperature is 50 ° C. while stirring and mixing. It was heated so that it might become. To this, 15.2 g of flaky sodium hydroxide was gradually added over 2 hours, and the mixture was further stirred for 6 hours while maintaining the internal temperature of 50 ° C. (Formulation B). After cooling the resulting solution to room temperature, the precipitated salt was removed by filtration, and further epichlorohydrin and water mixed by vacuum distillation were removed to obtain the following chemical formula (7);

A terminal glycidylation product of IPN10 represented by (IPEG10), unreacted IPN10, the following chemical formula (8);

A by-product 1 corresponding to the compound (B-1) represented by the formula:

As a result, 199.4 g of an intermediate-containing composition (1-1) containing by-product 2 corresponding to the compound (B-2) represented by formula (1) was obtained.
Next, 30.1 g of the intermediate-containing composition (1-1) and 14.5 g of a 30% trimethylamine hydrochloride aqueous solution were charged all at once into a 100 mL four-necked flask equipped with a stirring blade, a thermometer, and a condenser. The mixture was stirred at a temperature of 50 ° C. for 6 hours to obtain 44.6 g of a water-soluble monomer-containing composition (1-2) containing a cationic group-containing monomer (IPEC10). Next, 1.95 g of a water-soluble monomer-containing composition (1-2) containing IPEC10, 0.49 g of hydroxyethyl acrylate, and 9.40 g of pure water were charged into a 100 mL sample tube equipped with a stirrer, and mixed by stirring. However, the internal temperature was raised to 80 ° C. 0.42 g of 15% sodium persulfate aqueous solution was added here, and it stirred for 1 hour, maintaining internal temperature at 80 degreeC, and obtained 12.26g of polymers (1-3). The obtained polymer confirmed that the monomer was consumed using NMR and gas chromatography. An adsorption test on mud was conducted using the obtained polymer.
Table 1 shows the charged molar ratio and formulation of the reaction raw materials charged to obtain the intermediate-containing composition (1-1). Table 1 shows the IPN10, IPEG10, and secondary ingredients contained in the obtained intermediate-containing composition (1-1). Amount of organism 1 and by-product 2, polymerization test conducted using water-soluble monomer-containing composition (1-2), and adsorption to mud conducted using polymer (1-3) The test results are shown in Table 2.

(Example 2)
In a 5 L four-necked flask equipped with a stirring blade, a thermometer, and a condenser tube, 1679.8 g of an ethylene oxide average 10-mole adduct of isoprenol (IPN10, hydroxyl value: 106.5 mgKOH / g) and epichlorohydrin (ECH) 1406.0 g were added. The mixture was charged in a lump and heated to an internal temperature of 50 ° C. while stirring and mixing. To this, 374.3 g of 48% aqueous sodium hydroxide solution was added dropwise over 2 hours, and the mixture was further stirred for 4 hours while maintaining the internal temperature of 50 ° C. During the reaction, the system was evacuated to carry out the reaction while distilling off water (prescription A). After cooling the resulting solution to room temperature, the precipitated salt was removed by washing with water, and further epichlorohydrin and water mixed by vacuum distillation were removed to remove the terminal glycidylated product of IPN10 (IPEG10), unreacted 1732.0 g of an intermediate-containing composition (2-1) containing IPN10, by-product 1 and by-product 2 was obtained.
Next, in a 2 L four-necked flask equipped with a stirring blade, a thermometer, and a cooling tube, 1100.0 g of the intermediate-containing composition (2-1) and 532.6 g of a 30% trimethylamine hydrochloride aqueous solution were charged all at once. While mixing, the mixture was stirred at an internal temperature of 50 ° C. for 6 hours to obtain 1632.6 g of a water-soluble monomer-containing composition (2-2) containing a cationic group-containing monomer (IPEC10). Next, in a 100 mL sample tube equipped with a stirrer was charged 2.03 g of the water-soluble monomer-containing composition (2-2) containing IPEC10, 0.51 g of hydroxyethyl acrylate, and 9.66 g of pure water, and the mixture was stirred and mixed. However, the internal temperature was raised to 80 ° C. 0.44 g of 15% sodium persulfate aqueous solution was added thereto, and the mixture was stirred for 1 hour while maintaining the internal temperature at 80 ° C., to obtain 12.64 g of the polymer (2-3). The obtained polymer confirmed that the monomer was consumed using NMR and gas chromatography. An adsorption test on mud was conducted using the obtained polymer.
Table 1 shows the charged molar ratio and formulation of the reaction raw materials charged in order to obtain the intermediate-containing composition (2-1). Table 1 shows the IPN10, IPEG10, and secondary ingredients contained in the obtained intermediate-containing composition (2-1). Amount of organism 1, by-product 2, polymerization test performed using water-soluble monomer-containing composition (2-2), and adsorption to mud performed using polymer (2-3) The test results are shown in Table 2.

(Example 3)
In a 2 L four-necked flask equipped with a stirring blade, a thermometer, and a condenser tube, 802.0 g of an ethylene oxide average 10-mole adduct of isoprenol (IPN10, hydroxyl value: 106.5 mgKOH / g) and epichlorohydrin (ECH) 422.1 g were added. The mixture was charged in a lump and heated to an internal temperature of 50 ° C. while stirring and mixing. 91.2 g of flaky sodium hydroxide was gradually added thereto over 2 hours, and the mixture was further stirred for 5 hours while maintaining the internal temperature of 50 ° C. (Formulation B). After cooling the resulting solution to room temperature, the precipitated salt was removed by filtration, and further epichlorohydrin and water mixed by vacuum distillation were removed to obtain a terminal glycidylated product of IPN10 (IPEG10), unreacted IPN10. Then, 833.3 g of an intermediate-containing composition (3-1) containing by-product 1 and by-product 2 was obtained.
Next, 30.0 g of the intermediate-containing composition (3-1) and 16.5 g of a 30% trimethylamine hydrochloride aqueous solution were charged all at once into a 100 mL four-necked flask equipped with a stirring blade, a thermometer, and a cooling tube. The mixture was stirred at a temperature of 50 for 6 hours to obtain 46.5 g of a water-soluble monomer-containing composition (3-2) containing a cationic group-containing monomer (IPEC10). Next, 2.36 g of a water-soluble monomer-containing composition (3-2) containing IPEC10, 0.53 g of hydroxyethyl acrylate, and 10.25 g of pure water are charged into a 100 mL sample tube equipped with a stirrer, and mixed by stirring. However, the internal temperature was raised to 80 ° C. 0.46 g of 15% sodium persulfate aqueous solution was added thereto, and the mixture was stirred for 1 hour while maintaining the internal temperature at 80 ° C., to obtain 13.60 g of the polymer (3-3). The obtained polymer confirmed that the monomer was consumed using NMR and gas chromatography. An adsorption test on mud was conducted using the obtained polymer.
Table 1 shows the charged molar ratio and formulation of the reaction raw materials charged to obtain the intermediate-containing composition (3-1). Table 1 shows the IPN10, IPEG10, and secondary components contained in the obtained intermediate-containing composition (3-1). Amount of organism 1, by-product 2, polymerization test conducted using water-soluble monomer-containing composition (3-2), and adsorption to mud conducted using polymer (3-3) The test results are shown in Table 2.

(Comparative Example 1)
In a 500 mL four-necked flask equipped with a stirring blade, a thermometer, and a condenser tube, 300.3 g of an isoprenol ethylene oxide average 10-mole adduct (IPN10, hydroxyl value: 106.5 mgKOH / g) and epichlorohydrin (ECH) 79.2 g were added. The mixture was charged in a lump and heated to an internal temperature of 50 ° C. while stirring and mixing. To this, 22.8 g of flaky sodium hydroxide was gradually added over 2 hours, and the mixture was further stirred for 4 hours while maintaining the internal temperature of 50 ° C. (Formulation B). After cooling the resulting solution to room temperature, the precipitated salt was removed by filtration, and further epichlorohydrin and water mixed by vacuum distillation were removed to obtain a terminal glycidylated product of IPN10 (IPEG10), unreacted IPN10. 274.8 g of an intermediate-containing composition (4-1) containing By-product 1 and By-product 2 was obtained.
Next, 30.0 g of the intermediate-containing composition (4-1) and 13.3 g of a 30% trimethylamine hydrochloride aqueous solution were charged all at once into a 100 mL four-necked flask equipped with a stirring blade, a thermometer, and a cooling tube. The mixture was stirred at a temperature of 50 ° C. for 6 hours to obtain 43.3 g of a water-soluble monomer-containing composition (4-2) containing a cationic group-containing monomer (IPEC10). Next, 1.97 g of a water-soluble monomer-containing composition (4-2) containing IPEC10, 0.48 g of hydroxyethyl acrylate, and 9.04 g of pure water are charged into a 100 mL sample tube equipped with a stirrer, and mixed by stirring. However, the internal temperature was raised to 80 ° C. 0.41 g of 15% sodium persulfate aqueous solution was added thereto, and the mixture was stirred for 1 hour while maintaining the internal temperature at 80 ° C., to obtain 11.90 g of the polymer (4-3). The obtained polymer confirmed that the monomer was consumed using NMR and gas chromatography. An adsorption test on mud was conducted using the obtained polymer.
Table 1 shows the charged molar ratio and formulation of the reaction raw materials charged to obtain the intermediate-containing composition (4-1). Table 1 shows IPN10, IPEG10, Amount of living thing 1, by-product 2, polymerization test conducted using water-soluble monomer-containing composition (4-2), and adsorption to mud conducted using polymer (4-3) The test results are shown in Table 2.
The abbreviations in Tables 1 and 1 are as follows.
IPN10: ethylene oxide average 10 mol adduct of isoprenol ECH: epichlorohydrin NaOH: sodium hydroxide IPEG10: terminal glycidated product of IPN10 IPEG10 content: mass ratio of IPEG10 contained in the intermediate-containing composition IPN10 content: Proportion of IPN10 contained in 1 byproduct 1: molar ratio of byproduct 1 corresponding to compound (B-1) with respect to IPEG10 and molar ratio with respect to the total amount of IPEG10 and IPN10 byproduct 2: compound (B- 2) The molar ratio of the by-product 2 corresponding to 2) with respect to IPEG 10 and the molar ratio with respect to the total amount of IPEG 10 and IPN 10 total: the total amount of by-product 1 and by-product 2 contained in the intermediate-containing composition , Molar ratio to IPEG10, and Molar ratio to the total amount of PEG10 and IPN10

From the results of Tables 1 and 2, the following was found.
In the intermediate-containing composition for a water-soluble monomer containing the compound (A), the content of the compound (B) in the composition is 0.1 to 6.0 with respect to the content of the compound (A). It has been demonstrated that when the polymer is produced using a monomer-containing composition derived from the composition, it can be prevented from being remarkably gelled. Furthermore, it has also been demonstrated that a polymer produced using a monomer-containing composition derived from such a composition has an excellent adsorption capacity for mud.
In addition, in the said Example, in the case of the synthesis | combination of a compound (A), the ethylene oxide average 10 mol addition product of isoprenol was used as a compound (I), epichlorohydrin as an epihalohydrin, and sodium hydroxide as an alkali compound, respectively. A by-product contained in the corresponding compound (B) is generated, but the content of the compound (B) by-produced during the synthesis of the compound (A) is set to a specific range, so that gelation during the polymerization reaction occurs. The same mechanism can be used when a polymerization reaction is carried out using a monomer-containing composition derived from an intermediate-containing composition for water-soluble monomers containing a specific amount of compound (B). In addition, the polymer produced using the monomer-containing composition derived from the composition having a specific content of the compound (B) has an excellent adsorption capacity for mud. Mechanism shown are all in the compound (B) was produced using the derived monomer-containing composition from a water-soluble monomer-body intermediate containing composition comprising a specific weight polymers as well. Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in this specification, and can exhibit advantageous effects.

The cationic group-containing monomer and the reaction intermediate were quantified by liquid chromatography under the conditions described in <Quantification of intermediate composition> above. The weight average molecular weight and dye migration preventing ability of the polymer were measured according to the following methods.

<Quantitative determination method of ethylene oxide adduct of isoprenol>
Quantification of the ethylene oxide adduct of isoprenol was performed by high-speed chromatography under the following conditions.
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L Disodium hydrogen phosphate.12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength 215 nm).

<Quantitative determination of N-vinylpyrrolidone>
The measurement of N-vinylpyrrolidone was performed using liquid chromatography under the following conditions.
Column: manufactured by Shiseido Co., Ltd. CAPCELL PAK C18 TYPE UG120 5 μm, 1.5 mmΦ × 250 mm
Eluent: methanol / water = 1/24 (containing 0.4% by mass of sodium 1-heptanesulfonate)
Flow rate: 100 μL / min
Column oven: 20 ° C
Injection volume: 10 μL
UV detector: 235 nm.

<Measurement conditions of weight average molecular weight>
Device: Hitachi L-7000 Series Detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 ml / min.
Calibration curve: POLYETHYLENGLYCOL STANDARD made by GL Sciences Inc.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio).

<Measurement of solid content>
In an oven heated to 130 ° C. in a nitrogen atmosphere, the polymer of the present invention (1.0 g of the polymer composition of the present invention plus 1.0 g of water) was allowed to stand for 1 hour for drying treatment. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.

<Measurement method of dye transfer prevention ability>
(I) JIS cotton cloth (5 cm × 5 cm, obtained from the Japan Standards Association) was measured in advance using a colorimetric color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. with a reflectance (before the test) The whiteness of the test cloth).
(Ii) Hard water was prepared by adding pure water to calcium chloride dihydrate and magnesium chloride hexahydrate (calcium ion 150 ppm (calcium carbonate equivalent), magnesium ion (magnesium carbonate equivalent) 50 ppm).
(Iii) Polyoxyethylene (2) Sodium lauryl ether sulfate 3.2 g, Polyoxyethylene (7) Lauryl ether 0.4 g, Sodium borate 0.4 g, Citric acid 1.0 g 0.0 g, and an aqueous surfactant solution was prepared. The pH was adjusted to 8.5 with sodium hydroxide.
(Iv) A targot meter is set at 40 ° C., 500 mL of hard water, 0.7 g of zeolite, 7.7 g of 5% by mass sodium carbonate aqueous solution, 3.5 g of 5% by mass LAS (obtained from Kao Corporation), 3.5 g of solid In a minute conversion, 3.5 g of a 1% polymer aqueous solution and 2 g of a 0.25 mass% aqueous solution of chlorazole black LF (reagent obtained from Tokyo Chemical Industry Co., Ltd.) as a dye were put in a pot and stirred at 100 rpm for 1 minute. Then, 10 white cloths were put and stirred at 100 rpm for 30 minutes.
(V) The white cloth was drained by hand, and 500 mL of tap water adjusted to 40 ° C. was placed in the pot and stirred at 100 rpm for 2 minutes. This was done twice.
(Vi) After applying the cloth to a white cloth and drying it while stretching the wrinkles with an iron, the whiteness of the white cloth was measured again with the above colorimetric color difference meter (the whiteness of the test cloth after washing). Called degrees).
(Vii) From the above measurement results, the ability to prevent dye transfer was determined by the following equation.
(Viii) Transfer prevention ability (%) = [(whiteness of test cloth after washing) / (whiteness of test cloth before test)] × 100

<Method for evaluating compatibility with surfactant>
A detergent composition containing a test sample (polymer or polymer composition) was prepared with the following formulation.
SFT-70H (manufactured by Nippon Shokubai Co., Ltd., polyoxyethylene alkyl ether); 40 g
Neoperex F-65 (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate); 7.7 g (active ingredient 5 g)
Coatamine 86W (manufactured by Kao Corporation, stearyltrimethylammonium chloride); 17.9 g (active ingredient 5 g)
Diethanolamine; 5g
Ethanol; 5 g
Propylene glycol; 5g
Test sample (solid content conversion): 1.5 g
Ion-exchanged water; balance (the amount of ion-exchanged water is appropriately adjusted so that the total amount is 100 g, with the amount of test sample used as the actual usage)
Thoroughly stir the components so that they are uniform, and the turbidity value at 25 ° C. is measured using a turbidimeter (“NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.) and Turbidity (kaolin turbidity mg / l) Measured with

The following compounds were used as the polyalkylene glycol chain-containing monomer represented by the general formula (12).
Isoprenol ethylene oxide average 10 mol adduct (hereinafter also referred to as “IPN10”): hydroxyl value 106.5 (mgKOH / g)
Isoprenol ethylene oxide average 25 mol adduct (hereinafter also referred to as “IPN25”): hydroxyl value 47.3 (mgKOH / g)
Isoprenol ethylene oxide average 50 mol adduct (hereinafter also referred to as “IPN50”): hydroxyl value 25.5 (mgKOH / g)

Example 4
A 200 ml four-necked flask equipped with a stirring blade, thermometer, and cooling tube was charged with 100 g of IPN10, 52.7 g (0.57 mol) of epichlorohydrin, and 3.1 g (0.01 mol) of tetrabutylammonium bromide in a lump, and mixed by stirring. While heating, the internal temperature was 40-50 ° C. To this, 7.6 g (0.19 mol) of pelletized sodium hydroxide (hereinafter also referred to as “NaOH”) was gradually added over 30 minutes, and while maintaining the internal temperature of 45 to 50 ° C., further 5 Stir for 5 hours. After cooling the resulting solution to room temperature, the precipitated salt was removed by filtration, and epichlorohydrin and water mixed by vacuum distillation were further removed to obtain 102 g of a reaction solution containing 78.5 g of an intermediate product. Obtained at a rate of 70 mol%. Further, from ¹ H-NMR, it was confirmed that the intermediate product [A] of the monomer (1) shown in FIG. 3 was formed (that is, in the general formula (19) below, n is an average of 10). Compound).

Next, a 200 ml four-necked flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel was charged with 13.0 g (0.14 mol) of trimethylamine hydrochloride and 7.0 g (0.39 mol) of pure water and stirred. While mixing, the internal temperature was raised to 50 ° C. Here, 85.0 g of a reaction solution containing 65.0 g of the intermediate product [A] was slowly added dropwise over 3 hours while maintaining the internal temperature of 50 ° C., and further stirred for 3 hours. Thus, an aqueous solution of the monomer (1) was obtained. As a result of analysis by high performance liquid chromatography, the yield was 95 mol%. Moreover, the production | generation of the monomer (1) shown in FIG. 4 was confirmed also from < ¹ > H-NMR (namely, in the following general formula (20), the compound of the structure where n is an average 10).

(Example 5)
A 200 ml four-necked flask equipped with a stirring blade, a thermometer, and a condenser tube was charged with 100 g of IPN25, 23.3 g (0.25 mol) of epichlorohydrin, and 1.4 g (4.4 mmol) of tetrabutylammonium bromide in a lump and stirred and mixed. While heating, the internal temperature was 45-50 ° C. To this, 3.4 g (0.084 mol) of pellet-like NaOH was gradually added over 30 minutes, and the mixture was further stirred for 5.5 hours while maintaining the internal temperature of 40 to 50 ° C. After cooling the obtained solution to room temperature, the precipitated salt is removed by filtration, and further, epichlorohydrin and water mixed by vacuum distillation are removed to obtain a reaction solution containing 73.4 g of the intermediate product [B]. Obtained 95.3 g, yield 70 mol%. The formation was confirmed from ¹ H-NMR as in Example 1 (that is, a compound having a structure in which n is 25 on average in the general formula (19)).

Next, 5.6 g (0.060 mol) of trimethylamine hydrochloride and 3.1 g (0.17 mol) of pure water were charged into a 200 ml four-necked flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel and stirred. While mixing, the internal temperature was raised to 50 ° C. 85.0 g of the reaction solution containing 66 g of the intermediate product [B] was slowly added dropwise over 3 hours while maintaining the internal temperature of 50 ° C., and further stirred for 3 hours. Thus, an aqueous solution of the monomer (2) was obtained. As a result of analysis by high performance liquid chromatography, the reaction proceeded quantitatively and the yield was 95 mol%. The production was confirmed from ¹ H-NMR as in Example 1 (that is, a compound having a structure in which n is 25 on average in the general formula (20)).

(Example 6)
A 200 ml four-necked flask equipped with a stirring blade, thermometer, and cooling tube was charged with 100 g of IPN50, 12.3 g (0.13 mol) of epichlorohydrin, and 0.72 g (2.3 mmol) of tetrabutylammonium bromide in a lump, and mixed with stirring. While heating, the internal temperature was 40-50 ° C. Here, 1.8 g (0.044 mol) of pellet-like NaOH was gradually added over 30 minutes, and the mixture was further stirred for 5.5 hours while maintaining the internal temperature of 40 to 50 ° C. After cooling the resulting solution to room temperature, the deposited salt is removed by filtration, and epichlorohydrin and water mixed by vacuum distillation are removed to obtain a reaction solution containing 72.5 g of the intermediate product [C]. Obtained 94.1 g, yield 70 mol%. The production was confirmed from ¹ H-NMR in the same manner as in Example 1 (that is, a compound having a structure in which n is 50 on average in the general formula (19)).

Next, trimethylamine hydrochloride 3.0 g (0.032 mol) and pure water 1.6 g (0.089 mol) were charged into a 200 ml four-necked flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel and stirred. While mixing, the internal temperature was raised to 50 ° C. Here, 85.0 g of a reaction solution containing 65.9 g of the intermediate product [C] was slowly added dropwise over 3 hours while maintaining the internal temperature of 50 ° C., and further stirred for 3 hours. Thus, an aqueous solution of the monomer (3) was obtained. As a result of analysis by high performance liquid chromatography, the reaction proceeded quantitatively and the yield was 95 mol%. The production was confirmed from ¹ H-NMR in the same manner as in Example 1 (that is, a compound having a structure in which n is 50 on average in the general formula (20)).

(Example 7)
In a 200 ml four-necked flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, 100 g of IPN10 and 0.306 g (0.002 mol) of 46% boron trifluoride-diethyl ether complex were placed. While stirring at an internal temperature of 80 ° C., 18.2 g (0.19 mol) of epichlorohydrin was added dropwise over 2 hours, followed by further stirring for 4 hours. Thus, an intermediate product [D] of monomer (1) was obtained. As a result of analysis by high performance liquid chromatography, the yield was 60 mol%.

Next, 108.0 g of the intermediate product [D] of monomer (1) was charged into a 200 ml four-necked flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, and stirred at an internal temperature of 70 ° C. Then, 35.5 g (0.18 mol) of 30% trimethylamine aqueous solution was added dropwise over 1 hour, followed by further stirring for 6 hours. Thus, an aqueous solution of the monomer (1) was obtained. As a result of analysis by high performance liquid chromatography, the yield was 62%. The production was confirmed from ¹ H-NMR in the same manner as in Example 1 (that is, a compound having a structure in which n is an average of 10 in the general formula (20)).

(Polymerization example 1)
A glass separable flask having a capacity of 2000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 1040.5 g of pure water, 158.8 g of monomer (1), and 15.9 g of IPN10, while stirring. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 33-3.4 g of N-vinylpyrrolidone (hereinafter, also referred to as “NVP”), 2,2′-azobis (2-methylpropionamidine) dihydro hydride in a polymerization reaction system maintained at 90 ° C. with stirring. 112.9 g of a 15% aqueous solution of chloride (hereinafter also referred to as “15% V50”) was dropped from each separate nozzle. The dropping time of each solution was 180 minutes for NVP and 190 minutes for 15% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (1) was obtained.
The weight average molecular weight of the polymer (1) was 18,500, and the number average molecular weight was 8,800.

(Polymerization example 2)
A glass separable flask having a capacity of 2000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 972.3 g of pure water, 111.1 g of monomer (1), and 22.2 g of IPN10, and while stirring, The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 333.4 g of NVP and 109.7 g of 15% V50 were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. The dropping time of each solution was 180 minutes for NVP and 190 minutes for 15% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (2) was obtained.
The weight average molecular weight of the polymer (2) was 19,800, and the number average molecular weight was 7,400.

(Polymerization Example 3)
A glass separable flask having a capacity of 2000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 906.9 g of pure water, 69.5 g of monomer (2), and 27.8 g of IPN25 while stirring. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 333.4 g of NVP and 103.3 g of 15% V50 were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. The dropping time of each solution was 180 minutes for NVP and 190 minutes for 15% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (3) was obtained.
The weight average molecular weight of the polymer (3) was 16,400, and the number average molecular weight was 6,800.

(Polymerization example 4)
A glass separable flask having a capacity of 2000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 909.7 g of pure water, 69.5 g of monomer (3), and 27.8 g of IPN50, while stirring. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 333.4 g of NVP and 101.8 g of 15% V50 were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. The dropping time of each solution was 180 minutes for NVP and 190 minutes for 15% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (4) was obtained.
The polymer (4) had a weight average molecular weight of 15,100 and a number average molecular weight of 6,200.

(Polymerization Example 5)
A glass separable flask having a capacity of 3000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 1081.6 g of pure water, 555.7 g of monomer (3), and 55.6 g of IPN50 while stirring. The temperature was raised to 0 ° C. to obtain a polymerization reaction system. Next, 333.4 g of NVP and 111.7 g of 15% V50 were dropped from separate nozzles into the polymerization reaction system maintained at 90 ° C. with stirring. The dropping time of each solution was 180 minutes for NVP and 190 minutes for 15% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of NVP, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (5) was obtained.
The weight average molecular weight of the polymer (1) was 8,300, and the number average molecular weight was 3,500.

(Polymerization Example 6)
In a glass separable flask having a capacity of 2000 mL equipped with a reflux condenser and a stirrer, 448.5 g of pure water was charged, and the temperature was raised to 90 ° C. while stirring. Next, in a polymerization reaction system maintained at 90 ° C., 258.0 g of methyl acrylate (hereinafter also referred to as AM), 143.3 g of monomer (1), 57.3 g of IPN10, 15 while stirring. 68.6 g of% sodium persulfate (hereinafter also referred to as NaPS) and 58.8 g of 35% sodium bisulfite (hereinafter also referred to as SBS) were dropped from separate nozzles. The dropping time was 180 minutes for AM, 120 minutes for monomer (1), 120 minutes for IPN10, 190 minutes for 15% NaPS and 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of AM, the reaction solution was kept at 90 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (6) was obtained.

(Polymerization Example 7)
In a glass separable flask having a capacity of 2000 mL equipped with a reflux condenser and a stirrer, 219.6 g of pure water was charged and heated to 90 ° C. while stirring. Next, while stirring in a polymerization reaction system maintained at 90 ° C., 355.3 g of 60% acrylamide aqueous solution (hereinafter referred to as 60% AAm), 118.5 g of monomer (1), IPN10 47. 4 g, 15% NaPS 67.1 g, and 35% SBS 57.5 g were added dropwise from separate nozzles. The dropping time was 180 minutes for 60% AAm, 120 minutes for monomer (1), 120 minutes for IPN10, 190 minutes for 15% NaPS and 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of 60% AAm, the reaction solution was kept at 90 ° C. for 30 minutes (ripening) to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (7) was obtained.

(Polymerization Example 8)
In a glass separable flask having a capacity of 3000 mL equipped with a reflux condenser and a stirrer, 900.9 g of pure water was charged and heated to 90 ° C. while stirring. Next, while stirring in a polymerization reaction system maintained at 90 ° C., 348.0 g of 2-hydroxyethyl acrylate (hereinafter also referred to as HEA), 580.0 g of monomer (3), IPN50 58.0 g 15% NaPS 67.3 g and 35% SBS 57.7 g were added dropwise from separate nozzles. The dropping time was 180 minutes for HEA, 150 minutes for monomer (3), 150 minutes for IPN50, 190 minutes for 15% NaPS and 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of HEA, the reaction solution was kept at 90 ° C. for 30 minutes (ripening) to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (8) was obtained.

(Polymerization Example 9)
In a glass separable flask having a capacity of 2000 mL equipped with a reflux condenser and a stirrer, 623.6 g of pure water was charged and heated to 65 ° C. while stirring. Next, while stirring in a polymerization reaction system maintained at 65 ° C., 333.4 g of vinyl acetate (hereinafter also referred to as VAc), 55.6 g of monomer (2), 22.2 g of IPN25, and 102.6 g of 15% V50 was dropped from separate nozzles. The dropping time was 180 minutes for VAc, 150 minutes for monomer (2), 150 minutes for IPN25, and 190 minutes for 15% V50. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the addition of VAc, the reaction solution was kept at 65 ° C. (ripening) for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool. In this way, an aqueous solution of the polymer (9) was obtained.

(Comparative polymerization example 1)
In a 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade), 475.0 g of pure water 10.0 g, 60% aqueous solution of diallyldimethylammonium chloride (hereinafter also referred to as 60% DADMAC), 15.0 g of methyl methacrylate (hereinafter also referred to as MMA) was charged, and the temperature was raised to the boiling point while stirring to prepare a polymerization reaction system. Next, 38.3 g of 15% NaPS and 13.5 g of a 35% disodium disulfite aqueous solution (hereinafter also referred to as 35% MBS) were added to separate nozzles in the polymerization reaction system maintained at the boiling point under stirring. More dripped. The dropping time of each solution was 190 minutes for 15% NaPS, and 30 minutes for 35% MBS after adjusting to 95 ° C. after completion of dropping of 15% NaPS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of 35% MBS, the above reaction solution was kept at 95 ° C. for 30 minutes (ripening) to complete the polymerization. After completion of the polymerization, 335.3 g of pure water was added and diluted while stirring and allowing the polymerization reaction liquid to cool. In this way, an aqueous solution of the comparative polymer (1) was obtained.

(Example 8)
Polyvinylpyrrolidone K30 (manufactured by Wako Pure Chemical Industries, Ltd.) which is a homopolymer of N-vinylpyrrolidone (referred to as VP) as the polymers (1) to (5), the comparative polymer (1) and the comparative polymer (2) Were evaluated for the ability to prevent dye transfer according to the above method. The results are summarized in Table 3.

As is apparent from Table 3, the polymer in the present invention has significantly superior dye transfer preventing ability and compatibility with a surfactant as compared with conventional comparative polymers. It was revealed that the cationic group-containing monomer of the present invention can be preferably used as a raw material for these polymers.
In the above examples, a cationic group-containing monomer having a specific structure is used as one kind of monomer component in the synthesis of the polymer, but it is represented by the general formula (11). The mechanism by which a polymer synthesized using a cationic group-containing monomer as a monomer component exhibits excellent dye transfer preventing ability and compatibility with a surfactant is the cation represented by the general formula (11). The same applies to polymers synthesized using a monomer having a functional group as a monomer component. Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in this specification, and can exhibit advantageous effects.

Claims (13)

The following general formula (1);

(Wherein, ^{R 0} is .R ¹ representing the methylation group, .Y ¹ which represents a methylene group or an ethylene group are the same or different, is .n representing an alkylene group having 2 to 20 carbon atoms, oxy An intermediate-containing composition for a water-soluble monomer comprising a compound (A) represented by an average added mole number of an alkylene group (—Y ¹ —O—) and representing a number of 5 to 300. There,
The composition has the following general formula (2):

(Wherein, ^{R 0} are the same or different, .R ¹ representing the methylation groups are the same or different, .X representing the methylene group or an ethylene ^{_{group, -CH 2 -CH (OR 2)}} -CH _2- O- or a direct bond, R ² represents a hydrogen atom or a glycidyl group, Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, and n is an oxyalkylene group. (-Y ¹ —O—) is the average addition mole number, which is the same or different and represents a number of 5 to 300), and further containing the compound (B) The amount is 0.1 to 6.0 mol% based on the content of the compound (A),
Content of this compound (A) is 50-100 mass% with respect to 100 mass% of non volatile matters of the intermediate containing composition for water-soluble monomers, The intermediate for water-soluble monomers characterized by the above-mentioned Body-containing composition. The compound (A) is represented by the following general formula (I):

(Wherein, ^{R 0} is .R ¹ representing the methylation group, .Y ¹ which represents a methylene group or an ethylene group are the same or different, is .n representing an alkylene group having 2 to 20 carbon atoms, oxy Obtained by reacting compound (I) represented by an alkylene group (—Y ¹ —O—) with an average addition mole number of 5 to 300, and epihalohydrin,
In the water-soluble monomer intermediate-containing composition, the content of the compound (B) is 0.1 to 5.0 mol% with respect to the total content of the compound (A) and the compound (I). Yes,
The total content of the compound (A) and the compound (I) is 50 to 100% by mass with respect to 100% by mass of the nonvolatile content of the intermediate-containing composition for a water-soluble monomer. The intermediate-containing composition for a water-soluble monomer according to claim 1. The following general formula (1);

(Wherein, ^{R 0} is .R ¹ representing the methylation group, .Y ¹ which represents a methylene group or an ethylene group are the same or different, is .n representing an alkylene group having 2 to 20 carbon atoms, oxy An intermediate-containing composition for a water-soluble monomer comprising a compound (A) represented by an average added mole number of an alkylene group (—Y ¹ —O—) and representing a number of 5 to 300) A method of manufacturing comprising:
The production method comprises the following general formula (I):

(Wherein, ^{R 0} is .R ¹ representing the methylation group, .Y ¹ which represents a methylene group or an ethylene group are the same or different, is .n representing an alkylene group having 2 to 20 carbon atoms, oxy Compound (I) represented by an alkylene group (—Y ¹ —O—) and represented by an average number of moles of 5 to 300, and epihalohydrin are 1/2 to 1/15 (compound ( A method for producing an intermediate-containing composition for a water-soluble monomer, comprising a step of reacting at a molar ratio of hydroxyl group / epihalohydrin) of I). The method for producing an intermediate-containing composition for a water-soluble monomer according to claim 3, wherein the reaction step includes a step of reacting compound (I) with epihalohydrin in the presence of an alkali compound. 4. The intermediate for water-soluble monomer according to claim 3, wherein the reaction step includes a step of adding an epihalohydrin and a Lewis acid catalyst to compound (I) and then reacting with an alkali compound. 5. A method for producing a body-containing composition. A water-soluble monomer-containing composition obtained by reacting the intermediate-containing composition for a water-soluble monomer according to claim 1 or 2 with a functional group-containing compound,
The water-soluble monomer is a cationic group-containing monomer obtained by using a tertiary amine salt represented by the following general formula (15) as the functional group-containing compound. A monomer-containing composition.

(Wherein R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkenyl group, and R ² and R ³ are bonded to form a cyclic structure) And X ¹ − represents a counter ion.) A water-soluble monomer-containing composition obtained by reacting the intermediate-containing composition for a water-soluble monomer according to claim 1 or 2 with a functional group-containing compound,
The water-soluble monomer is an amino group-containing monomer obtained by using a secondary amine represented by the following general formula (16) as the functional group-containing compound. Containing composition.

Wherein R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkenyl group, and R ² and R ³ are bonded to form a cyclic structure. May be.) A water-soluble monomer-containing composition obtained by reacting the intermediate-containing composition for a water-soluble monomer according to claim 1 or 2 with a functional group-containing compound,
The water-soluble monomer-containing composition, wherein the water-soluble monomer is a sulfonic acid group-containing monomer obtained using a sulfite compound as the functional group-containing compound. A water-soluble monomer-containing composition obtained by reacting the intermediate-containing composition for a water-soluble monomer according to claim 1 or 2 with a functional group-containing compound,
The water-soluble monomer-containing composition, wherein the water-soluble monomer is an alkyl ether group-containing monomer obtained using a hydroxyl group-containing alkyl compound as the functional group-containing compound. The following general formula (11);

(Wherein R ⁰ represents a C H ₃ group, R ¹ represents a CH ₂ group or a CH ₂ CH ₂ group, and R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom or a carbon atom. Represents an alkyl group, an aryl group or an alkenyl group having ^{1 to} 20 carbon atoms, Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms, and n represents an oxyalkylene group (—Y ¹ —O—). A cationic group-containing monomer, characterized in that it represents an average added mole number, is a number of 5 to 300, and X ¹ − represents a counter anion. (I) the following general formula (12);

(In the formula, R ⁰ represents a C H ₃ group, R ¹ represents a CH ₂ group or a CH ₂ CH ₂ group, and Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. , N represents the average number of added moles of the oxyalkylene group (—Y ¹ —O—), and represents a number of 5 to 300). Reaction of a monomer having an ethylene glycol chain represented by epihalohydrin and an alkali compound A step (step A) of
(Ii) a cationic group-containing monomer comprising a step (step B) of reacting the reaction product obtained in step A with a tertiary amine salt represented by the following general formula (15) Body manufacturing method.

(Wherein R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkenyl group, and R ² and R ³ are bonded to form a cyclic structure) And X ¹ − represents a counter ion.) (I) the following general formula (12);

(In the formula, R ⁰ represents a C H ₃ group, R ¹ represents a CH ₂ group or a CH ₂ CH ₂ group, and Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. , N represents an average added mole number of an oxyalkylene group (—Y ¹ —O—) and represents a number of 5 to 300.), a polyalkylene glycol chain-containing monomer, an epihalohydrin, and an alkali compound. A step of reacting (step A);
(Ii) a step of reacting the reaction product obtained in the step A with a secondary amine represented by the following general formula (16) (step C);
(Iii) a step of reacting the reaction product obtained in Step C with a quaternizing agent of any one of alkyl halide, benzyl halide, dialkyl sulfate, and alkyl sulfonate (Step D). A method for producing a cationic group-containing monomer.

Wherein R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkenyl group, and R ² and R ³ are bonded to form a cyclic structure. May be.) (I) the following general formula (12);

(In the formula, R ⁰ represents a C H ₃ group, R ¹ represents a CH ₂ group or a CH ₂ CH ₂ group, and Y ¹ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. , N represents the average number of added moles of the oxyalkylene group (—Y ¹ —O—), and represents a number of 5 to 300) and an epihalohydrin in the presence of a catalyst. A step of reacting (step E);
(Ii) a cationic group-containing monomer comprising a step (step F) of reacting the reaction product obtained in step E with a tertiary amine represented by the following general formula (17) Manufacturing method.

(Wherein R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkenyl group, and R ² and R ³ are bonded to form a cyclic structure) May be formed.)

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