JP7236055B2 - Diallylamine/diallyl ether copolymer, production method and use thereof - Google Patents

Description

The present invention relates to a novel copolymer, more specifically, it has an excellent balance of adhesion to substrates such as metals and resins, and various performances such as heat resistance, and is optionally imparted with cationic properties. It relates to a diallylamine/diallyl ether copolymer that can be suitably used for specific applications by

So-called diallylamine-based (co)polymers, which have structural units derived from diallylamines, can be easily synthesized in an aqueous solution, and are widely industrially manufactured. It has been used for applications such as surface modification (see, for example, Patent Document 1).
However, the adhesiveness to substrates such as metals and resins may not always be sufficient depending on the application, and further improvement of the adhesiveness to these substrates is desired. In addition, even higher performance has been required for other performance such as heat resistance.

On the other hand, it has been reported that (co)polymers derived from diallyl ether compounds such as 2-(allyloxymethyl)methyl acrylate also have excellent heat resistance and adhesion to substrates (for example, Patent Documents 2).
However, even these (co)polymers do not necessarily have sufficient adhesion to metal substrates such as aluminum and stainless steel, and some resin substrates, and there is a need to improve adhesion to these substrates. was wanted. In addition, in relation to some uses, it has been desired to improve the degree of freedom in design so that cationic properties and the like can be imparted.

JP 2004-115675 A JP 2014-040585 A

In view of the background art described above, an object of the present invention is to provide a novel copolymer having an excellent balance between adhesion to substrates such as metals and resins and performance such as heat resistance.
As a result of intensive studies, the present inventors have found that by combining a diallylamine-based structural unit having a specific structure with a diallyl ether-based structural unit having a specific structure, adhesion to various substrates such as metals and resins can be achieved. , heat resistance, etc., can be realized at a high level, and have completed the present invention.

（但し、上記式（Ｉａ）及び（Ｉｂ）中、Ｒ^１は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基である。）、並びに
下記の構造式（ＩＩａ）で示される構造を有する構成単位（ＩＩ）少なくとも１種、

（但し、上記式（ＩＩａ）中、Ｒ^２は、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。）、
を有する、高分子化合物、である。 That is, the first invention of the present application is
[1]
At least one structural unit (I) having a structure represented by the following structural formula (Ia) or (Ib), or a structure that is an addition salt or quaternary ammonium salt thereof

(In formulas (Ia) and (Ib) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms. ), and at least one structural unit (II) having a structure represented by the following structural formula (IIa),

(wherein, in the above formula (IIa), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent);
A polymer compound having

（但し、上記式（Ｉａ’）、及び（Ｉｂ’）中、Ｒ^１は、式（Ｉａ）及び（Ｉｂ）において定義されるものと同様であり、Ｒ^１’は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基であり、Ｒ^１とＲ^１’とは、同一であっても異なっていてもよく、Ｘ^－はカウンターイオンである。）、 Hereinafter, [2] and [3] are preferred aspects or embodiments of the first invention of the present application.
[2]
The polymer compound according to [1], wherein the proportion of the structural unit (I) is 0.1 to 50 mol% and the proportion of the structural unit (II) is 99.9 to 50 mol%.
[3]
The polymer compound according to [1] or [2], wherein the structural unit (I) is an addition salt having a structure represented by the following structural formula (Ia') or (Ib').

(However, in the above formulas (Ia') and (Ib'), R ¹ is the same as defined in formulas (Ia) and (Ib), and R ¹ ' has a hydrogen atom or a hydroxyl group. an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having ⁷ to ¹⁰ carbon atoms, which ^may be is an ion.),

（但し、上記式（ＩＩＩ）中、Ｒ^１は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基である。）、並びに、
下記の構造式（ＩＶ）で示される構造を有する単量体（２）から導かれる構成単位（ｉｉ）少なくとも１種、

（但し、上記式（ＩＶ）中、Ｒ^２は、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。）、
を有する、高分子化合物、である。 The second invention of the present application is
[4]
At least one structural unit (i) derived from a monomer (1) having a structure represented by the following structural formula (III), or a structure that is an addition salt or quaternary ammonium salt thereof;

(In formula (III) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.), and
at least one structural unit (ii) derived from a monomer (2) having a structure represented by the following structural formula (IV);

(wherein, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent);
A polymer compound having

Hereinafter, [5] is a preferred aspect or embodiment of the second invention of the present application, and [6] is a preferred aspect or embodiment of the first and second inventions of the present application.
[5]
The polymer compound according to [4], wherein the proportion of structural unit (i) is 0.1 to 50 mol% and the proportion of structural unit (ii) is 99.9 to 50 mol%.
[6]
The polymer compound according to any one of [1] to [5], which has a weight average molecular weight of 10,000 or more.

（但し、上記式（ＩＩＩ）中、Ｒ^１は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基である。）、並びに、
下記の構造式（ＩＶ）で示される構造を有する単量体（２）少なくとも１種、

（但し、上記式（ＩＶ）中、Ｒ^２は、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。）、
を共重合する工程を有する、高分子化合物の製造方法である。 The third invention of the present application is
[7]
at least one monomer (1) having a structure represented by the following structural formula (III), or a structure that is an addition salt or quaternary ammonium salt thereof;

(In formula (III) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.), and
at least one monomer (2) having a structure represented by the following structural formula (IV);

(wherein, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent);
A method for producing a polymer compound, comprising the step of copolymerizing

Hereinafter, [8] to [10] are preferred aspects or embodiments of the third invention of the present application, and [11] is preferred aspects or embodiments of the first and second inventions of the present application.
[8]
The polymer compound according to [7], wherein the molar ratio of monomer (1) and monomer (2) to be subjected to the above step is within the range of 0.1:99.9 to 90:10. manufacturing method.
[9]
The method for producing a polymer compound according to [7] or [8], wherein the above steps are carried out in at least one solvent selected from the group consisting of dimethylformamide, tetrahydrofuran and toluene.
[10]
The above step is carried out by dropping the monomer (2) into an organic solvent in which the monomer (1) is dissolved in advance. A method for producing a molecular compound.
[11]
A coating material, an adhesive, an adhesive, a surface modifier, a resist, a dye fixing agent, an ink fixing agent, and a pigment dispersant, comprising the polymer compound according to any one of [1] to [6]. , flocculants, antibacterial agents, bactericides, paper strength agents, corrosion inhibitors, plating brighteners or optical materials.

According to the present invention, a novel diallylamine/diallyl ether copolymer is realized that has both adhesion to various substrates such as metals and resins and various performances such as heat resistance at a high level.
In addition, according to the production method of the present invention, a production method is provided that can produce a novel diallylamine-based/diallyl ether-based copolymer with high efficiency and high quality.
Furthermore, according to one aspect of the present invention, various uses are provided that take advantage of the excellent properties of such novel diallylamine/diallyl ether copolymers.

上記式（Ｉａ）及び（Ｉｂ）中、Ｒ^１は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基である。

上記式（ＩＩａ）中、Ｒ^２は、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。 The first invention of the present application The copolymer of the first invention of the present application is a structural unit having a structure represented by the following structural formula (Ia) or (Ib), or an addition salt or quaternary ammonium salt structure thereof. (I) is a polymer compound having at least one structural unit (II) having a structure represented by the following structural formula (IIa).

In formulas (Ia) and (Ib) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.

In formula (IIa) above, R ² is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 4 carbon atoms.

Structural unit (I)
Structural unit (I) (hereinafter also referred to as "diallylamine-based structural unit (I)") constituting a part of the polymer compound of the first invention of the present application has the structural formula (Ia) or (Ib) or its addition salt or quaternary ammonium salt structure.
By having the structural unit (I), the polymer compound of the first invention of the present application has excellent adhesion to various substrates, and, if necessary or desired, can have cationic properties and an effect of suppressing silica scale. Easy.

In the polymer compound of the first invention of the present application, the ratio of diallylamine-based structural units (I) to all structural units is preferably 0.1 to 50 mol%, more preferably 0.5 to 30 mol%. More preferably, 1 to 20 mol % is particularly preferable. When the ratio of the structural unit (I) is within the above range, it becomes easier to realize excellent adhesion to various substrates, cationic properties, silica scale suppressing effect, and the like.
The ratio of the diallylamine-based structural unit (I) in the polymer compound of the first invention of the present application can be measured by elemental analysis, for example, by analyzing the combustion gas of the polymer compound by anion chromatography. More specifically, it can be measured, for example, by the method described in the examples of the present specification.
Further, in a practical copolymer production process, once the production conditions are established to some extent, the structural unit (I) can be determined from the monomer composition of the starting materials without analyzing the composition of the copolymer step by step. The ratio can be estimated with considerable accuracy.

The ratio of the structural unit (I) in the polymer compound of the first invention of the present application can be appropriately increased or decreased by adjusting the monomer composition in the starting materials. Moreover, it is also possible to appropriately adjust by changing the polymerization conditions such as the order in which the monomers are brought into contact with each other.

ここで、水酸基を有していてもよい炭素数１から１０のアルキル基は直鎖状、分岐状、環状のいずれであってもよく、その好ましい例としては、水酸基を有していてもよい炭素数１から４のアルキル基、具体的にはメチル基、エチル基、ｎ－プロピル基、イソプロピル基、各種ブチル基、２－ヒドロキシエチル基、２－ヒドロキシプロピル基、３－ヒドロキシプロピル基などを、さらにはシクロヘキシル基などを挙げることができる。また、炭素数７から１０のアラルキル基の好ましい例としては、ベンジル基、フェネチル基などを挙げることができる。 As described above, in the structural formulas (Ia) and (Ib) representing one form of the structural unit (I), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.

Here, the alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group may be linear, branched or cyclic, and a preferred example thereof may have a hydroxyl group. Alkyl groups having 1 to 4 carbon atoms, specifically methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, etc. , and further a cyclohexyl group. Preferable examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group.

上記式（Ｉａ’）、及び（Ｉｂ’）中、Ｒ^１は、式（Ｉａ）及び（Ｉｂ）において上記にて定義したものと同様であり、Ｒ^１’は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基であり、Ｒ^１とＲ^１’とは、同一であっても異なっていてもよく、Ｘ^－はカウンターイオンである。
カウンターイオンは一価のアニオンであればよく、その種類は特に限定されないが、有機酸又は無機酸由来のアニオンであることが好ましく、特に好ましくは、ハロゲンイオン（さらに好ましくは、Ｃｌ^－、Ｂｒ^－、若しくはＩ^－）、メチル硫酸イオン、エチル硫酸イオン、又は酢酸イオンである。 Further, as the addition salt or quaternary ammonium salt of the structure represented by the structural formula (Ia) or (Ib), those having the structure represented by the following structural formula (Ia') or (Ib') is preferred.

In formulas (Ia') and (Ib') above, R ¹ is the same as defined above in formulas (Ia) and (Ib), and R ¹ ' has a hydrogen atom and a hydroxyl group. an alkyl group having 1 to 10 carbon atoms which may be substituted, or an aralkyl group having 7 to 10 carbon atoms, wherein R ¹ and R ¹ ' may be the same or different, and X ^- is a counter ion is.
The counter ion is not particularly limited as long as it is a monovalent anion, but it is preferably an anion derived from an organic acid or an inorganic acid, particularly preferably a halogen ion (more preferably Cl ⁻ , Br ⁻ , or I ⁻ ), methyl sulfate, ethyl sulfate, or acetate.

Preferred addition salts include, for example, hydrochlorides, hydrobromides, sulfates, nitrates, sulfites, phosphates, amidosulfates, methanesulfonates, among others, amidosulfates, methanesulfonates. etc. are preferable from the viewpoint of solubility in a solvent.
Preferred quaternary ammonium salts include, for example, N,N-dimethylammonium chloride, N,N-diethylammonium chloride, N,N-dipropylammonium chloride, N,N-dibutylammonium chloride, N,N-methylbenzylammonium chloride, N,N-ethylbenzylammonium chloride, and bromides corresponding to these chlorides, iodides, methylsulfates, and the like, among which N,N-dimethylammonium chloride, N,N-diethylammonium chloride, etc. is preferable from the viewpoint of solubility in a solvent.

The polymer compound of the first invention of the present application may have only one type of diallylamine-based structural unit (I), or may have two or more types of diallylamine-based structural units (I). When it has two or more types of structural units (I), two or more types represented by the same general formula among the general formulas (structural formulas) (Ia), (Ib), (Ia′), and (Ib′) may be combined, or two or more types of structural units (I) represented by different general formulas may be combined.
When there are two or more types of structural units (I), they may be derived from different monomers, or may be derived from the same monomer. With respect to the latter, for example, a structural unit represented by structural formula (Ia) and a structural unit represented by structural formula (Ib) may both occur from the same diallyther monomer (1), The ratio can be appropriately adjusted depending on the polymerization conditions and the like. Further, when adding or changing an addition salt, only a part of the structural unit (I) may be added or changed, resulting in two or more types of structural units (I).

上記式（ＩＩａ）中、Ｒ^２は、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。炭素数１から４の炭化水素基は、直鎖状、分岐鎖状および環状のいずれであってもよく、エーテル結合を含んでいてもよい。 Structural unit (II)
Structural unit (II) (hereinafter also referred to as "diallyl ether-based structural unit (II)") constituting a part of the polymer compound of the first invention of the present application has a structure represented by the following structural formula (IIa): have.
The structure represented by the following structural formula (IIa), which characterizes the diallyl ether-based structural unit (II), has a ring structure (tetrahydrofuran ring) in the main chain, so that the polymer compound of the first invention of the present application has excellent heat resistance. Moreover, since it has methylene groups on both sides of the tetrahydrofuran ring, it is possible to impart excellent flexibility to the polymer compound of the first invention of the present application.

In formula (IIa) above, R ² is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group having 1 to 4 carbon atoms may be linear, branched or cyclic, and may contain an ether bond.

Examples of the hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, vinyl group, allyl group and methallyl group. , crotyl group, cyclopropyl group, cyclobutyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, vinyloxyethyl group, epoxy group, oxetanyl group and the like, but are not limited thereto. .

Examples of the substituents include linear unsaturated hydrocarbon groups such as vinyl group, allyl group, methallyl group, and crotyl group; cyclic ether groups such as epoxy group, glycidyl group, and oxetanyl group; methoxy group, ethoxy group, alkoxy groups such as methoxyethoxy group; alkylthio groups such as methylthio group and ethylthio group; acyl groups such as acetyl group and propionyl group; acyloxy groups such as acetyloxy group and propionyloxy group; alkoxy groups such as methoxycarbonyl group and ethoxycarbonyl group carbonyl group; methylthiocarbonyl group, alkylthiocarbonyl group such as ethylthiocarbonyl group; fluorine atom, chlorine atom, bromine atom, halogen atom such as iodine atom; ureido group; amide group; cyano group; but not limited to these.

Among these options for R ² , the monomer (2) leading to the diallyl ether-based structural unit (II) can be industrially produced advantageously, and the viscosity of the monomer (2) can be lowered, and the dilutability From the viewpoint of improving the Preferably, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, allyl group, methallyl group, crotyl group, methoxyethyl group, ethoxyethyl group, glycidyl group and a vinyloxyethyl group are more preferable, and chain saturated carbonization having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group Hydrogen groups are more preferred, methyl, ethyl, n-propyl, isopropyl and tert-butyl groups are even more preferred, and methyl and ethyl groups are particularly preferred.

In the polymer compound of the first invention of the present application, the proportion of the diallyl ether-based structural unit (II) in all structural units is preferably 99.9 to 50 mol%, more preferably 99.5 to 70 mol%. is more preferred, and 99 to 80 mol % is particularly preferred. When the ratio of the structural unit (II) is within the above range, it becomes easier to achieve excellent adhesion to various substrates, high heat resistance, and the like.
The ratio of the diallyl ether-based structural unit (II) in the polymer compound of the first invention of the present application can be measured, for example, by analyzing the combustion gas of the polymer compound by anion chromatography, and is more specific. can be measured, for example, by the method described in Examples of the present specification.
In a practical copolymer production process, once the production conditions are established to some extent, the structural unit (II) can be determined from the monomer composition of the starting materials without analyzing the composition of the copolymer step by step. The ratio can be estimated with considerable accuracy.
The proportion of the structural unit (II) in the polymer compound of the first invention of the present application can be appropriately increased or decreased by adjusting the monomer composition in the starting materials. Moreover, it is also possible to appropriately adjust by changing the polymerization conditions such as the order in which the monomers are brought into contact with each other.

The polymer compound of the first invention of the present application may have only one type of diallyl ether-based structural unit (II), or may have two or more types of diallyl ether-based structural units (II).

Other Structural Units The polymer compound of the first invention of the present application may be composed only of the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II), or the structural unit (I) and the structural unit ( It may have structural units other than II).
Structural units other than the structural unit (I) and the structural unit (II) are not particularly limited. Structural units derived from monomers used in combination with system monomers can be used as appropriate.
Examples of the former include structural units derived from sulfur dioxide; various allylsulfonic acids; various amides such as acrylamide; various anionic monomers such as unsaturated carboxylic acids and unsaturated dicarboxylic acids; It is not limited to these.

Examples of the latter include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylic s-butyl acid, t-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, t-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid Lauryl, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (meth)acrylate 4-hydroxybutyl acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate , β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, α - (Meth)acrylic acid esters such as methyl hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate; (meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; Unsaturated monocarboxylic acids such as meth)acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; monosuccinic acid ( 2-acryloyloxyethyl), mono(2-methacryloyloxyethyl) succinate, unsaturated monocarboxylic acids in which the chain is extended between the unsaturated group and the carboxyl group; unsaturated monocarboxylic acids, such as maleic anhydride and itaconic anhydride Acid anhydrides; styrene, α-methyls Aromatic vinyls such as ethylene, vinyltoluene, methoxystyrene; N-substituted maleimides such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide; polystyrene, polymethyl (meth)acrylate, poly Macromonomers having a (meth)acryloyl group at one end of the polymer molecular chain, such as ethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; Acetic acid vinyl esters such as vinyl, vinyl propionate, vinyl butyrate, and vinyl benzoate; Vinyl ethers such as ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine , N-vinyl acetamide and the like; structural units derived from unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate, but are not limited thereto.
Among these, maleic acid, acrylic acid, and acrylamide are particularly preferably used.

As described above, in the diallylamine-based/diallyl ether-based copolymer of the first invention of the present application, the proportion of the structural unit (I) is 0.1 to 50 mol%, and the structural unit (II) is preferably 99.9 to 50 mol %.
The ratio of the structural unit (I) is 0.5 to 30 mol%, and the ratio of the structural unit (II) is more preferably 99.5 to 70 mol%, and the ratio of the structural unit (I) is 1 to 20 mol %, and the proportion of the structural unit (II) is particularly preferably 99 to 80 mol %.
Regarding the ratio of diallylamine-based structural unit (I) to diallyl ether-based structural unit (II), the molar ratio of diallyl ether-based structural unit (II)/diallylamine-based structural unit (I) is 2.3 to 200.0. is preferred, and 4.0 to 100.0 is particularly preferred.

Diallyl ether-based monomers generally exhibit higher radical polymerizability than diallylamine-based monomers. Therefore, conventionally, even if an attempt is made to copolymerize the two, the polymerization proceeds only with the diallyl ether-based monomer. A homopolymer consisting only of the diallyl ether structural unit (II) was obtained. From this point of view, the diallylamine/diallyl ether copolymer of the present invention is a novel polymer. The diallylamine-based/diallyl ether-based copolymer of the present embodiment, which has a 200.0, is a copolymer that exceeds predictions from the prior art.
In addition, in the first invention of the present application, the molar ratio of the diallyl ether-based structural unit (II)/diallylamine-based structural unit (I) is not limited to the preferred range described above, and the diallyl ether-based structural unit (II) and the diallylamine-based structural unit (I) in a desired copolymer composition.

The molecular weight of the diallylamine-based/diallyl ether-based copolymer of the first invention of the present application is not particularly limited, and a copolymer having a suitable molecular weight may be appropriately polymerized in relation to the required physical properties and applications.
Preferably, the diallylamine/diallyl ether copolymer of the first invention of the present application has a weight average molecular weight (Mw) of 5,000 or more, more preferably 5,000 to 500,000, particularly preferably 10,000 to 100,000.
The molecular weight of the diallylamine/diallyl ether copolymer can be measured by the GPC method when it is soluble in the eluent. (Mw) can be measured.
The molecular weight of the copolymer of the first invention of the present application can be adjusted by adjusting the types and compositions of the essential and optional monomers, the temperature, time and pressure in the polymerization process, the type and amount of the radical initiator used in the polymerization process, etc. It can be adjusted as appropriate.

The diallylamine-based/diallyl ether-based copolymer of the first invention of the present application may have the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II) as described above, and other structural units or may have no other structural units.
The ratio of the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II) in the total structural units of the diallylamine-based/diallyl ether-based copolymer is not particularly limited, but should be 25 to 100 mol%. is preferred, and 50 to 100 mol % is more preferred.
When the ratio of the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II) is within the above range, adhesion, heat resistance, cohesiveness, dispersibility, and solvent solubility based on these structural units etc. can be realized more easily.
The composition of the diallylamine-based/diallyl ether-based copolymer, including the ratio of the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II), depends on the polymerization conditions, especially the composition of the monomers supplied for polymerization. It can be adjusted as appropriate.

上記式（ＩＩＩ）中、Ｒ^１は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基である。

上記式（ＩＶ）中、Ｒ^２は、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。 The second invention of the present application The copolymer of the second invention of the present application comprises a monomer (1) having a structure represented by the following structural formula (III), an addition salt thereof, or a quaternary ammonium salt structure: at least one derived structural unit (i), and
It is a polymer compound having at least one structural unit (ii) derived from a monomer (2) having a structure represented by the following structural formula (IV).

In formula (III) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.

In formula (IV) above, R ² is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 4 carbon atoms.

The diallylamine/diallyl ether copolymer of the second invention of the present application is a monomer (1 ) (hereinafter also referred to as “diallylamine-based structural unit (i)”) and at least one monomer (2) having a structure represented by the following structural formula (IV): It is a polymer compound having at least one structural unit (ii) derived from (hereinafter also referred to as "diallyl ether-based structural unit (ii)"). That is, the diallylamine-based/diallyl ether-based copolymer of the second invention of the present application only needs to have a diallylamine-based structural unit (i) and a diallyl ether-based structural unit (ii), and has other structural units. or may have no other structural unit.

In the diallylamine-based/diallyl ether-based copolymer of the second invention of the present application, the ratio of the structural unit (i) is 0.1 to 50 mol%, and the ratio of the structural unit (ii) is 99.9. It is preferably ~50 mol %. It is more preferable that the proportion of structural unit (i) is 0.5 to 30 mol%, and the proportion of structural unit (ii) is 99.5 to 70 mol%, and the proportion of structural unit (i) is is 1 to 20 mol %, and the proportion of the structural unit (ii) is particularly preferably 99 to 80 mol %.
Regarding the ratio of diallylamine-based structural unit (i) and diallyl ether-based structural unit (ii), the molar ratio of diallyl ether-based structural unit (ii)/diallylamine-based structural unit (i) is 2.3 to 200.0. is preferred, and 4.0 to 100.0 is particularly preferred.

Diallyl ether-based monomers generally exhibit higher radical polymerizability than diallylamine-based monomers, so conventionally, polymerization proceeds only with diallyl ether-based monomers, and diallyl ether-based structural units (ii) A homopolymer of only From this point of view, the diallylamine/diallyl ether copolymer of the second invention of the present application is also a novel polymer. The diallylamine-based/diallyl ether-based copolymer of the present embodiment, which has a ratio of 3 to 200.0, is a copolymer that exceeds expectations from the prior art.
In the second invention of the present application, the molar ratio of the diallyl ether-based structural unit (ii)/the diallylamine-based structural unit (i) is not limited to the preferred range described above, and the diallyl ether-based structural unit (ii) and the diallylamine-based structural unit (i) in a desired copolymer composition.

The proportion of the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii) in the total structural units of the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application is determined by elemental analysis, for example, It can be measured by analyzing the combustion gas by anion chromatography, and more specifically, for example, by the method described in the examples of the present specification.

The molecular weight of the diallylamine-based/diallyl ether-based copolymer of the second invention of the present application is not particularly limited, and a copolymer having a suitable molecular weight may be appropriately polymerized in relation to the required physical properties and applications.
Preferably, the diallylamine/diallyl ether copolymer of the present invention has a weight average molecular weight (Mw) of 5,000 or more, more preferably 5,000 to 500,000, particularly preferably 10,000 to 100,000.
The molecular weight of the diallylamine/diallyl ether copolymer can be measured by the GPC method when it is soluble in the eluent. (Mw) can be measured.

The diallylamine-based/diallyl ether-based copolymer of the second invention of the present application only needs to have the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii), and has other structural units. or may have no other structural unit.
The ratio of the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii) in the diallylamine-based/diallyl ether-based copolymer of the second invention of the present application is not particularly limited, but is 25 to 100 mol%. is preferred, and 50 to 100 mol % is more preferred.
When the ratio of the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii) is within the above range, adhesion, heat resistance, cohesiveness, dispersibility, and solvent solubility based on these structural units etc. can be realized more easily.
The composition of the diallylamine-based/diallyl ether-based copolymer, including the ratio of the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii), depends on the polymerization conditions, particularly the composition of the monomers supplied for polymerization. It can be adjusted as appropriate.

上記式（ＩＩＩ）中、Ｒ^１は、既述の構造式（Ｉａ）及び（Ｉｂ）におけるものと同様であり、より具体的には、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基である。これらの中でＲ^１として好ましい基も、既述の構造式（Ｉａ）及び（Ｉｂ）におけるＲ^１について説明したものと同様である。また、構造式（ＩＩＩ）で示される構造の付加塩若しくは第４級アンモニウム塩として好ましいものも、上記の構造式（Ｉａ）及び（Ｉｂ）で示される構造の付加塩及び第４級アンモニウム塩に関して説明したものと同様である。 Diallylamine-based structural unit (i) and diallylamine-based monomer (1)
The diallylamine-based structural unit (i), which is an essential structural unit of the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application, is a structure represented by the following structural formula (III), or an addition salt thereof, or a quaternary It is derived from a monomer (1) having a structure that is an ammonium salt (hereinafter also referred to as "diallylamine-based monomer").

In the above formula (III), R ¹ is the same as in the structural formulas (Ia) and (Ib) described above, and more specifically, a hydrogen atom or a carbon number that may have a hydroxyl group. to 10 alkyl groups, or C7 to C10 aralkyl groups. Preferred groups for R ¹ among these are also the same as those described for R ¹ in structural formulas (Ia) and (Ib). Also preferred as addition salts or quaternary ammonium salts of structures represented by structural formula (III) are the addition salts and quaternary ammonium salts of structures represented by structural formulas (Ia) and (Ib) above: Similar to what has been described.

In deriving the diallylamine-based structural unit (i), the diallylamine-based monomer (1) may be used alone or in combination of two or more. Using only one type of diallylamine-based monomer (1) is often advantageous in terms of cost and ease of control of the polymerization process. It is often advantageous in that it imparts desired properties to

上記式（ＩＶ）中、Ｒ^２は、既述の構造式（ＩＩａ）におけるものと同様であり、より具体的には、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。この中でＲ^２として好ましい基も、既述の構造式（ＩＩａ）におけるＲ^２について説明したものと同様である。 Diallyl ether-based structural unit (ii) and diallyl ether-based monomer (2)
The diallyl ether-based structural unit (ii), which is an essential structural unit of the diallylamine-based/diallyl ether-based copolymer of the second invention of the present application, is a monomer having a structure represented by the following structural formula (IV) (2) ( Hereinafter, it is also referred to as a “diallyl ether-based monomer”.).

In the above formula (IV), R ² is the same as in the structural formula (IIa) described above, more specifically, a hydrogen atom or optionally substituted carbon atoms of 1 to 4 is a hydrocarbon group of Among these, preferred groups for R ² are also the same as those described for R ² in structural formula (IIa).

In deriving the diallyl ether-based structural unit (ii), the diallyl ether-based monomer (2) may be used singly or in combination of two or more. Using only one type of diallyl ether-based monomer (2) is often advantageous in terms of cost and ease of control of the polymerization process. It is often advantageous in that it imparts desired properties to the coalescence.

Note that, depending on the polymerization conditions, the structural unit (ii) derived from the diallyl ether-based monomer (2) is not only the structural unit (II) having the structure represented by the structural formula (IIa) described above, but also the following may contain a structural unit having a structure represented by the structural formula (IIb) of

上記式（ＩＶ）中、Ｒ^２は、既述の構造式（ＩＩａ）におけるものと同様であり、より具体的には、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。この中でＲ^２として好ましい基も、既述の構造式（ＩＩａ）におけるＲ^２について説明したものと同様である。

In the above formula (IV), R ² is the same as in the structural formula (IIa) described above, more specifically, a hydrogen atom or optionally substituted carbon atoms of 1 to 4 is a hydrocarbon group of Among these, preferred groups for R ² are also the same as those described for R ² in structural formula (IIa).

In this case, the ratio of the structural units (II) having the structure represented by the structural formula (IIa) to the total structural units (ii) derived from the diallyl ether-based monomer (2) is 70 mol% or more. preferably 90 mol % to 100 mol %. When the ratio of the structural unit (II) having the structure represented by the structural formula (IIa) is 70 mol% or more, it becomes easy to achieve excellent heat resistance due to the tetrahydrofuran ring, and the structural formula ( It is possible to effectively suppress cross-linking and gelation due to the branched structure resulting from the structure shown in IIb).
The ratio of the structural unit (II) having the structure represented by the structural formula (IIa) to the total diallyl ether-based structural units (ii) can be appropriately adjusted by the polymerization conditions, especially by using a specific chain transfer agent. can be done.

Other Structural Units Structural units other than the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii), which can constitute the copolymer of the second invention of the present application, are the same as those described for the first invention of the present application. , and the preferred examples thereof are also the same as those described for the first invention of the present application.

（但し、上記式（ＩＩＩ）中、Ｒ^１は、水素原子、水酸基を有していてもよい炭素数１から１０のアルキル基、又は炭素数７から１０のアラルキル基である。）、並びに、
下記の構造式（ＩＶ）で示される構造を有する単量体（２）（以下、「ジアリルエーテル系単量体（２）」ともいう。）少なくとも１種、

（但し、上記式（ＩＶ）中、Ｒ^２は、水素原子、又は置換基を有していてもよい炭素数１から４の炭化水素基である。）、を共重合する工程を有する製造方法により製造されることが好ましい。 Method for producing diallylamine/diallyl ether copolymer The method for producing the diallylamine/diallyl ether copolymer of the present invention (the first and second inventions of the present application) is not particularly limited. It is preferably produced by a production method, and more specifically, a monomer (1) having a structure represented by the following structural formula (III), an addition salt thereof, or a quaternary ammonium salt structure: (hereinafter also referred to as “diallylamine-based monomer (1)”). At least one

(In formula (III) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.), and
at least one monomer (2) having a structure represented by the following structural formula (IV) (hereinafter also referred to as "diallyl ether-based monomer (2)");

(In formula (IV) above, R ² is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 4 carbon atoms.). It is preferably manufactured by

In the above production method, the ratio of the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) supplied to the copolymerization step is not particularly limited, and the desired diallylamine/diallyl ether The ratio can be appropriately set in consideration of the composition of the copolymer and the easiness of polymerization of the monomers (1) and (2). For example, after taking measures to reduce unreacted monomers, monomer (1) and monomer (2) are added at approximately the same ratio as the composition of the target diallylamine/diallyl ether copolymer. may be supplied, specifically, for example, so that the molar ratio of the monomer (1) and the monomer (2) is within the range of 0.1:99.9 to 50:50, Monomer (1) and monomer (2) can be provided. The molar ratio is preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80.
In general, the diallyl ether monomer (2) tends to undergo a polymerization reaction more easily than the diallylamine monomer (1). Alternatively, the ratio of the diallyl ether-based monomer (2) may be set lower and the ratio of the diallylamine-based monomer (1) may be set higher. In this case, the molar ratio of the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is preferably in the range of 70:30 to 90:10, preferably 80:20 to 90:10. It is more preferable to be within the range.

From the viewpoint of reaction uniformity, etc., the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is preferably carried out in a solvent.
The solvent used in the copolymerization step of the above embodiment is not particularly limited, and may be a polar solvent or a non-polar solvent, but a polar solvent is preferred.
Examples of polar solvents include water, inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, etc.) or aqueous solutions thereof, aqueous solutions of metal salts of inorganic acids (zinc chloride, calcium chloride, magnesium chloride, etc.), organic acids (formic acid, acetic acid, propionic acid, lactic acid, etc.) or aqueous solutions thereof, or polar organic solvents (alcohol, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, etc.), etc. Among these, polar organic solvents are preferred. Particularly preferably, at least one polar organic solvent selected from the group consisting of dimethylformamide, tetrahydrofuran and toluene can be used.
It is particularly preferable to use dimethylformamide because it has a high solubility in the diallyl ether-based monomer (2) and also dissolves the obtained diallylamine-based/diallyl ether-based copolymer well.
One type of these solvents may be used alone, or two or more types may be used in combination (mixed).

As a countermeasure for reducing the amount of unreacted monomers, the diallyl ether monomer (2) is added dropwise to an organic solvent in which the diallylamine monomer (1) is dissolved in advance. A step of copolymerizing (1) and (2) can be carried out. By adopting such a copolymerization step, the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) having different polymerizability can be obtained in good yields, and unreacted monomers can be eliminated. It can be copolymerized while reducing. This makes it easier to produce a diallylamine/diallyl ether copolymer having a desired composition and degree of polymerization with practical efficiency and cost.
In the dropping, the diallyl ether-based monomer (2) may also be dissolved in the solvent in advance.

The mechanism by which the above-mentioned advantageous effects are obtained by having the step of dropping the diallyl ether monomer (2) into an organic solvent in which the diallylamine monomer (1) is dissolved in advance is not necessarily clear. By sequentially dropping the diallyl ether-based monomer (2) with higher polymerizability into the solution of the diallylamine-based monomer (1) with lower polymerizability, the diallylamine-based monomer with lower polymerizability ( It is presumed that this has some relation to the fact that the polymerization can be carried out while maintaining the conditions in which 1) is always in a large excess.

The temperature at which the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is not particularly limited, but may be carried out within a temperature range of 50 to 120°C. is preferred, and it is particularly preferred to operate within the temperature range of 70 to 90°C. The pressure at that time is not particularly limited, but it is preferable to carry out at or near atmospheric pressure in consideration of cost and the like.

In the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2), it is preferable to use a polymerization initiator in order to promote the copolymerization reaction. The type of polymerization initiator is not particularly limited, and for example, a commonly used radical polymerization initiator can be used. Radical polymerization initiators generate radicals by heat or reducing substances to cause addition polymerization of polymerizable monomers, and include water-soluble or water-dispersible or oil-soluble persulfates, peroxides, There are azobis compounds and the like. Among them, water-soluble or water-dispersible azobis compounds are preferred, and 2,2'-azobis(2-methylpropyleneamidine) dihydrochloride, 2,2'-azobis(2-methylpropionate) dimethyl, etc. are preferably used. be able to.
The time for carrying out the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is not particularly limited. It is preferable to set the conditions, and 8 to 12 hours is particularly preferable. Further, when the diallyl ether-based monomer (2) is dropped into an organic solvent in which the diallylamine-based monomer (1) is dissolved in advance, a large excess of the diallylamine-based monomer (1) is maintained, From the viewpoint of stable polymerization reaction, the dropwise addition is preferably carried out over 1 to 4 hours, particularly preferably over 2 to 3 hours.

There are no particular restrictions on the concentration of the diallylamine-based monomer (1) and the concentration of the diallyl ether-based monomer (2) in the solvent in the copolymerization step, but from the viewpoint of performing stable and uniform copolymerization. Therefore, the concentration is preferably a certain value or less, and from the viewpoint of polymerization efficiency, the concentration is preferably a certain value or more. More specifically, the concentration of the diallylamine-based monomer (1) is 1.0×10 ⁻⁴ to . It is preferably 5.0×10 ⁻³ mol/g, particularly preferably 1.0×10 ⁻⁴ to 1.0×10 ⁻³ mol/g. The concentration of the diallyl ether monomer (2) in the dropwise solution is preferably 5.0×10 ⁻⁵ to 5.0×10 −3 mol/g, more preferably 1.0×10 ⁻³ to 2.0×10 ⁻³ mol/g. 0×10 ⁻³ mol/g is particularly preferred.
The amount of the polymerization initiator used is not particularly limited, but when a water-soluble or water-dispersible azobis compound is used as the polymerization initiator, the diallylamine monomer (1) and the diallyl ether monomer ( It is preferable to use 0.01 to 10 mol %, particularly preferably 0.5 to 2.0 mol %, based on the total of 2).

The diallylamine/diallyl ether copolymer obtained by the production method of the third invention of the present application preferably corresponds to the first or second invention of the present application, but is not limited thereto. Preferred forms of the copolymer when it corresponds to the first or second invention of the present application are the same as those described for the diallylamine-based/diallyl ether-based copolymer of the first or second invention of the present application. Therefore, the ratio of the diallylamine-based structural unit (I) in the diallylamine-based/diallyl ether-based copolymer obtained by the production method of the third invention of the present application is preferably 5 to 50 mol%, and the diallyl ether-based structural unit The ratio of (II) is preferably 95 to 50 mol %. The preferred molecular weight, intrinsic viscosity and the like are the same as those described above for the diallylamine/diallyl ether copolymers of the first and second inventions of the present application.

Applications, etc. The copolymers of the first and second inventions of the present application balance the excellent properties of the diallylamine-based polymer and the excellent properties of the diallyl ether-based polymer at a high level, or selectively Since it can be expressed, it can be suitably used for applications in which diallylamine-based (co)polymers or diallyl ether-based (co)polymers have conventionally been used.
Specifically, coating materials, adhesives, adhesives, surface modifiers, paper treatment agents, dyeing aids, dyeing fixatives, information recording materials such as optical materials, optical fiber materials, color filter resists, solder resists, plating Resist, insulator, sealant, inkjet ink, printing ink, paint, casting material, decorative plate, WPC, coating agent, photosensitive resin plate, dry film, lining agent, civil engineering and construction material, putty, repair material, floor paving material gel coat, overcoat, hand lay-up/spray-up, molding materials such as pultrusion, filament winding, SMC, BMC, polymer solid electrolytes, etc., but not limited to these.
As described above, the copolymers of the first and second inventions of the present application are particularly preferable because they can achieve both adhesion to various substrates such as metals and resins and various performances such as heat resistance at a high level. Applications include coating materials, adhesives, adhesives, surface modifiers, resists, and optical materials.
In addition, the copolymers of the first and second inventions of the present application can be imparted with cationic properties and silica scale inhibiting properties as desired. It can also be used particularly preferably in applications such as dispersants and flocculants.
It can also be suitably used for applications such as antibacterial agents, disinfectants, plating solutions, plating brighteners, corrosion inhibitors, and paper strength agents.

When the copolymers of the first and second inventions of the present application are used in the various applications described above, they may be used after removing the solvent used in the production of the copolymers, depending on the application. May be used with a solvent.
Further, one or more of various additives may be appropriately added as long as they do not contradict the purpose and purpose of the present invention. Examples of such additives include other resins, antioxidants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, plasticizers, fillers, tackifiers, colorants, pigments, dyes, Examples include, but are not limited to, conductive materials, antibacterial agents, disinfectants, plating solutions, corrosion inhibitors, and the like.

The present invention will be described in more detail below with reference to examples. It should be noted that the technical scope of the present invention is not limited by these examples in any way.

In the following examples/comparative examples, the following abbreviations may be used for convenience.
DADMAC: diallyldimethylammonium chloride MeAMA: methyl 2-(allyloxymethyl)acrylate DAMA-SA: diallylmethylamine sulfamate DAA-SA: diallylamine sulfamate DMF: dimethylformamide DAMA-HCl: methyldiallylamine hydrochloride DAA- HCl: diallylamine hydrochloride

In the following examples/comparative examples, physical properties and characteristics were evaluated and measured by the following methods.
(Weight average molecular weight)
The weight average molecular weight (M.W.) was measured by gel permeation chromatography (GPC) using a Hitachi L-2130 high performance liquid chromatograph.
The eluent channel pump was Hitachi L-2130, the detector was Hitachi L-2490 differential refractive index detector, and the column was two Shodex GPS K-805L (exclusion limit molecular weight: 4,000,000) connected in series. . The sample was adjusted to a concentration of 0.5 g/100 mL with the eluent, and 20 μL was used for the measurement. A dimethylformamide (DMF) solution was used as an eluent.
The measurement was performed at a column temperature of 40°C and a flow rate of 1.0 mL/min. A calibration curve was determined using polystyrene having a molecular weight of 10,200, 18,100, 37,900, 96,400, 427,000, etc. as a standard substance, and the weight average molecular weight (M.W.) of the copolymer was determined based on the calibration curve.
(Polymerization yield)
It was obtained from the peak area ratio obtained by the GPC method.
(Copolymer composition)
The copolymer solution obtained in each example/comparative example was diluted to 5 wt% using DMF, and anion analysis was performed using an anion chromatography Dionex ICS-1000 (manufactured by ThermoFisher) equipped with a combustion device. The molar ratio between diallylamines and MeAMA was calculated from the above.
(Heat-resistant)
The (co)polymer solution obtained in each example/comparative example was vacuum-dried for 24 hours to obtain a solid of each (co)polymer. Using a differential thermobalance Thermo plus 8120 (manufactured by Rigaku Co., Ltd.), the obtained solid was measured for weight loss and endothermic heat absorption under a nitrogen atmosphere at a heating rate of 5° C./min. In the obtained measurement data, the temperature at which the peak top of the first observed endothermic peak was reached was defined as the thermal decomposition temperature, which is an index of heat resistance.
(Adhesion)
The (co)polymer solution obtained in each example/comparative example was diluted with tetrahydrofuran (THF) so that the (co)polymer concentration was 5 wt%, and an aluminum test plate [manufactured by TP Giken Co., Ltd., table Symbol in 3: AL] was applied using a bar coder (No. 8), and then dried at 70°C for 30 minutes to obtain a coating film. Next, the adhesion of the coating film obtained above to an aluminum test plate was examined according to JIS K5600-5-6 (cross-cut method). In addition, when examining the adhesion, a total of 100 squares of 10 squares in the vertical direction and 10 squares in the horizontal direction were used. was evaluated for adhesion to the aluminum test plate.
Furthermore, instead of the aluminum test plate, a stainless steel test plate [manufactured by TP Giken Co., Ltd., symbol in Table 3: SUS], an ABS resin test plate [manufactured by Standard Test Piece Co., Ltd., symbol in Table 3: ABS], Polycarbonate test plate [manufactured by Standard Test Piece Co., Ltd., symbol in Table 3: PC], silicon wafer [manufactured by AS ONE Corporation, symbol in Table 3: SI], and ethylene vinyl acetate polymer test plate [Standard Co., Ltd. Test piece, symbol in Table 3: EVA] was used, and the adhesion to each test plate was evaluated in the same manner.
(cationic)
The (co)polymer solution obtained in each example/comparative example was diluted with THF so that the (co)polymer concentration was 5 wt %, and a bar coder ( No. 8) and then dried at 70° C. for 30 minutes to obtain a coating film. This coated substrate was immersed in an anionic dye solution (Coomassie Brilliant Blue R-250: 0.2 g, acetic acid: 20 g, methanol: 180 g) for 30 minutes at room temperature, washed with methanol and then dried. The degree of staining on the surface of the coating film after drying was visually observed and evaluated according to the following criteria.
◯: The entire coated surface is dyed with the dye.
Δ: Part of the coated surface is dyed with the dye.
x: The coated surface is hardly dyed with the dye.
(Silica scale suppression effect)
Anhydrous sodium metasilicate was added to pure water so that the silica concentration was 400 ppm, and after fractionating them, the (co)polymer synthesized in Examples/Comparative Examples was added as a scale inhibitor to a solid content concentration of 50 ppm. The test water was prepared as follows. Hydrochloric acid or sodium hydroxide was added to each test water to adjust the pH to 7.4 to 7.6. After 24 hours, the test water was sampled and filtered through a filter with a pore size of 0.45 μm. The concentration of ionic silica in the filtrate was measured, and the retention of ionic silica was determined by the following formula. The concentration of ionic silica was measured by the silicomolybdic acid method using a spectrophotometer UH5300 (manufactured by Hitachi High-Tech Science Co., Ltd.).

Example 1 (DADMAC:MeAMA=1:8, dropping polymerization)
6.06 g of DMF and 0.038 mol of diallyldimethylammonium chloride (DADMAC) were charged into a 300 mL separable flask equipped with a stirrer, a thermometer and a condenser. In a 200 mL pear-shaped flask, 0.300 mol of methyl 2-(allyloxymethyl)acrylate (MeAMA), 117.13 g of DMF and initiator V-601 (2,2′-azobis(2-methylpropionic acid) Dimethyl) 1.55 g (equivalent to 2 mol % relative to the monomer) was mixed under ice-cooling. The inner temperature of the separable flask was raised to 70° C., and the solution in the pear-shaped flask was added dropwise to initiate polymerization. The solution in the pear-shaped flask was added dropwise over 2 hours and 30 minutes. After 24 hours, the polymerization reaction was terminated and the GPC yield was 100%, M.P. W. : 13337 of a copolymer in the form of a cloudy viscous solution was obtained.
Tables 1 to 5 show the results of evaluating the copolymer composition, heat resistance, adhesion, cationic property, and silica scale inhibitory effect of the obtained copolymers.

Example 2 (DAMA-SA:MeAMA=1:8, dropping polymerization)
A 300 mL separable flask equipped with a stirrer, a thermometer and a condenser was charged with 6.06 g of DMF and 0.038 mol of diallylmethylamine sulfamate (DAMA-SA). In addition, 0.300 mol of MeAMA, 117.13 g of DMF, and 1.55 g of initiator V-601 (equivalent to 2 mol % of the monomer) were mixed in a 200 mL pear-shaped flask under ice cooling. The inner temperature of the separable flask was raised to 70° C., and the solution in the pear-shaped flask was added dropwise to initiate polymerization. The solution in the pear-shaped flask was added dropwise over 2 hours and 30 minutes. After 24 hours, the polymerization reaction was terminated and the GPC yield was 100%, M.P. W. : 14481 was obtained as a reddish brown solution copolymer.
Tables 1 to 4 show the results of evaluating the copolymer composition, heat resistance, adhesion and cationic properties of the obtained copolymers.

Example 3 (DAA-SA:MeAMA=1:8, dropping polymerization)
A 300 mL separable flask equipped with a stirrer, a thermometer and a condenser was charged with 6.06 g of DMF and 0.038 mol of diallylamine sulfamate (DAA-SA). In addition, 0.300 mol of MeAMA, 117.13 g of DMF, and 1.55 g of initiator V-601 (equivalent to 2 mol % of the monomer) were mixed in a 200 mL pear-shaped flask under ice cooling. The inner temperature of the separable flask was raised to 70° C., and the solution in the pear-shaped flask was added dropwise to initiate polymerization. The solution in the pear-shaped flask was added dropwise over 2 hours and 30 minutes. After 24 hours, the polymerization reaction was terminated and the GPC yield was 100%, M.P. W. : 15463 was obtained as a reddish brown solution copolymer.
Tables 1 to 4 show the results of evaluating the copolymer composition, heat resistance, adhesion and cationic properties of the obtained copolymers.

Example 4 (DADMAC:MeAMA=1:8, bulk polymerization)
A 20 mL test tube was charged with 12.69 g of DMF, 0.008 mol of MeAMA and 0.001 mol of DADMAC. The internal temperature of the test tube was raised to 50° C., and 0.04 g of initiator V-601 (equivalent to 2 mol % relative to the monomer) was added. After 24 hours, the polymerization reaction was terminated and a GPC yield of 95.78%, M.W. W. : 27952 was obtained as a colorless transparent solution-like copolymer.
Tables 1 to 3 show the results of evaluating the copolymer composition, heat resistance, and adhesion of the obtained copolymers.

Example 5 (DAMA-SA:MeAMA=1:8, bulk polymerization)
A 20 mL test tube was charged with 13.02 g of DMF, 0.008 mol of MeAMA and 0.001 mol of DAMA-SA. The internal temperature of the test tube was raised to 50° C., and 0.04 g of initiator V-601 (equivalent to 2 mol % relative to the monomer) was added. After 24 hours, the polymerization reaction was terminated and M.I. W. : 48621 was obtained as a yellow solution copolymer.
The GPC yield could not be calculated because the polymer peak and the DAMA-SA monomer peak overlapped.

Example 6 (DAA-SA:MeAMA=1:8, bulk polymerization)
A 20 mL test tube was charged with 12.90 g of DMF, 0.008 mol of MeAMA and 0.001 mol of DAA-SA. The internal temperature of the test tube was raised to 50° C., and 0.04 g of initiator V-601 (equivalent to 2 mol % relative to the monomer) was added. After 24 hours, the polymerization reaction was terminated and M.I. W. : 29710 was obtained as a pale yellow solution-like copolymer.
The GPC yield could not be calculated because the polymer peak and the DAA-SA monomer peak overlapped.

Comparative Example 1 (MeAMA, homopolymer)
A 20 mL test tube was charged with 7.27 g of DMF and 0.02 mol of MeAMA. The internal temperature of the test tube was raised to 50° C., and 0.06 g of initiator V-601 (equivalent to 2 wt % relative to the monomer) was added. After 24 hours, the polymerization reaction was terminated and the GPC yield was 100%, M.P. W. : 37521 was obtained as a colorless and transparent solution-like copolymer.
Tables 2 to 5 show the results of evaluation of heat resistance, adhesion, cationic properties, and silica scale inhibitory effect on the obtained polymers.

Reference Examples 1 to 3 (diallylamine-based homopolymer)
As Reference Examples 1 to 3, commercially available diallylamine homopolymers PAS-H-5L (DADMAC homopolymer), PAS-M-1 (DAMA-HCl homopolymer), and PAS- Table 2 shows the results of evaluating the heat resistance of 21Cl (DAA-HCl homopolymer).
Regarding Reference Example 1 (DADMAC homopolymer), the silica scale inhibitory effect was also evaluated. The results are shown in Table 5.

あらかじめをＤＡＤＭＡＣ溶解させたＤＭＦ中に、ＭｅＡＭＡを滴下した実施例１における共重合体組成は、一括重合を行なった実施例４と比較して、供給したＤＡＤＭＡＣ：ＭｅＡＭＡ組成により近く、より均一な組成の共重合体が得られたことを示す。同様に滴下重合を行なった実施例２及び３の共重合体組成も、一括重合を行なった実施例５及び６と比較して、より均一な組成の共重合体が得られた。

The copolymer composition in Example 1, in which MeAMA was added dropwise into DMF in which DADMAC was previously dissolved, was closer to the supplied DADMAC:MeAMA composition than in Example 4, in which batch polymerization was performed, and the composition was more uniform. It shows that a copolymer of was obtained. The copolymer compositions of Examples 2 and 3, in which the dropping polymerization was carried out in the same manner, also gave copolymers with a more uniform composition than those in Examples 5 and 6, in which the batch polymerization was carried out.

各実施例で得られた共重合体は、各参考例のジアリルアミン系単独重合体と比較して著しく高い分解温度を有し、比較例１のＭｅＡＭＡ単独重合体とほぼ同等のレベルにまで、耐熱性が大幅に向上していた。

The copolymer obtained in each example has a significantly higher decomposition temperature than the diallylamine-based homopolymer of each reference example, and has a heat resistance that is almost equivalent to that of the MeAMA homopolymer of Comparative Example 1. sex had improved significantly.

各実施例で得られた共重合体を用いた塗膜は、各種の金属、樹脂基材に対して、高い密着性を示した。特に、比較例１に示す様に従来のＭｅＡＭＡ単独重合体では必ずしも十分な密着性を実現することができなかったアルミニウム基材やステンレス基材に対しても、高い密着性を確実に実現することができた。

Coating films using the copolymers obtained in each example exhibited high adhesion to various metals and resin substrates. In particular, as shown in Comparative Example 1, it is possible to reliably realize high adhesion even to aluminum substrates and stainless steel substrates, which could not necessarily achieve sufficient adhesion with conventional MeAMA homopolymers. was made.

実施例１及び２の共重合体を用いた塗膜は、それぞれアニオン染料で染色が可能な染色性を有し、高いカチオン性を有していた。すなわち実施例１及び２に相当する実施形態の共重合体は、高いカチオン性を発現させることが可能であり、例えば染色性と耐熱性とを従来技術では実現し得なかったような高いレベルで両立させることができる。

The coating films using the copolymers of Examples 1 and 2 had dyeability capable of being dyed with anionic dyes and had high cationic properties. That is, the copolymers of the embodiments corresponding to Examples 1 and 2 are capable of exhibiting high cationic properties, for example, exhibiting high levels of dyeability and heat resistance that could not be achieved by conventional techniques. can be made compatible.

実施例１の共重合体を用いたスケール抑制剤は、参考例１のＤＡＤＭＡＣ単一重合体を用いたスケール抑制剤と同等のシリカスケール抑制効果を示し、比較例１の単一重合体を用いたスケール抑制剤よりも格段に優れたシリカスケール抑制効果を有していた。すなわち、実施例１に相当する実施形態の共重合体は、例えばシリカスケール抑制効果と耐熱性とを、従来技術では実現し得なかったような高いレベルで両立させることができる。

The scale inhibitor using the copolymer of Example 1 exhibited the same silica scale inhibitory effect as the scale inhibitor using the DADMAC homopolymer of Reference Example 1. It had a silica scale inhibitory effect that was significantly superior to that of inhibitors. That is, the copolymer of the embodiment corresponding to Example 1 can achieve, for example, both the effect of suppressing silica scale and heat resistance at a high level that could not be achieved by conventional techniques.

The diallylamine/diallyl ether copolymer of the present invention has both adhesion to various substrates such as resins and various performances such as heat resistance at a high level. For example, a diallylamine/diallyl ether copolymer having excellent properties can be produced with high efficiency and high quality. , and has high utility value and applicability in various industrial fields such as the information technology industry, the automobile industry, and the manufacture of daily necessities.

Claims (8)

At least one structural unit (I) having a structure represented by the following structural formula (Ia) or (Ib), or a structure that is an addition salt or quaternary ammonium salt thereof

(In formulas (Ia) and (Ib) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms. ), and at least one structural unit (II) having a structure represented by the following structural formula (IIa),

(wherein, in the above formula (IIa), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent);
wherein the proportion of the structural unit (I) is 0.1 to 50 mol% and the proportion of the structural unit (II) is 99.9 to 50 mol%. 2. The polymer compound according to claim 1 , wherein the structural unit (I) is an addition salt having a structure represented by the following structural formula (Ia') or (Ib').

(However, in the above formulas (Ia') and (Ib'), R ¹ is the same as defined in formulas (Ia) and (Ib), and R ¹ ' has a hydrogen atom or a hydroxyl group. an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having ⁷ to ¹⁰ carbon atoms, which ^may be is an ion.), 3. The polymer compound according to claim 1, which has a weight average molecular weight of 10,000 or more. at least one monomer (1) having a structure represented by the following structural formula (III), or a structure that is an addition salt or quaternary ammonium salt thereof;

(In formula (III) above, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.), and
at least one monomer (2) having a structure represented by the following structural formula (IV);

(wherein, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent);
A method for producing a polymer compound, comprising the step of copolymerizing the polymer compound according to claim 1 . 5. The polymer compound according to claim 4 , wherein the molar ratio of monomer (1) and monomer (2) to be subjected to the above step is within the range of 0.1:99.9 to 90:10. manufacturing method. 6. The method for producing a polymer compound according to claim 4 , wherein said step is carried out in at least one solvent selected from the group consisting of dimethylformamide, tetrahydrofuran and toluene. 7. The polymer compound according to any one of claims 4 to 6 , wherein the step is carried out by dropping the monomer (2) into an organic solvent in which the monomer (1) is dissolved in advance. manufacturing method. Coating materials, adhesives, pressure sensitive adhesives, surface modifiers, resists, dye fixing agents, ink fixing agents, pigment dispersants, and agglomeration comprising the polymer compound according to any one of claims 1 to 3 agents, antibacterial agents, disinfectants, paper strength agents, corrosion inhibitors, plating brighteners or optical materials.