Modified water-soluble polymer and method for producing same

Abstract

Provided are: a modified water-soluble polymer which has water solubility by having an amino group, has compatibility with a hydrophobic compound such as an oil by introducing a hydrophobic functional group thereinto, and is capable of effectively suppressing an increase in viscosity; and a method for producing the same. The above are achieved by means of a method for producing a modified water-soluble polymer, which includes: a step (I) for reacting a polymer (A) having a primary amino group with a carboxylic acid (B); and a step (II) for reacting the polymer (A) having the primary amino group with an allyl halide (C). In the step (I), 2-30 mol% of the total of the primary amino group and a secondary amino group of the polymer (A) having the primary amino group is acylated by the carboxylic acid (B). In the step (II), 20-70 mol% of the total of the primary amino group and the secondary amino group of the polymer (A) having the primary amino group is allylated by the allyl halide (C).

Description

Modified Water-Soluble Polymer and Method for Producing the Same

[0001] The present invention relates to a modified water-soluble polymer and a method for producing the same, and more specifically, to a modified water-soluble polymer which is water-soluble due to having amino groups, has hydrophobic functional groups introduced therein, and can suppress an increase in viscosity, and a method for producing the same.

[0002] Polymers having amino groups such as polyethyleneimine and polyallylamine are water-soluble due to the amino groups despite being polymers, and thus are used in various applications as water-soluble polymers. It is possible to further introduce hydrophobic functional groups into the above water-soluble polymer, whereby compatibility with hydrophobic compounds such as oil can also be imparted. For example, a hydrophobic group can be introduced by acylating the above water-soluble polymer. A water-soluble polymer having hydrophobic groups introduced therein has both water solubility and compatibility with oils and the like, and thus can be used in various applications such as fabric care compositions and acid corrosion inhibitors. (See, for example, Patent Documents 1 and 2.)

[0003] However, when acylation is performed according to the above technique, amide groups with high polarity are generated, and bonding between acylated water-soluble polymer molecules becomes strong, which increases the viscosity of the aqueous polymer solution and may make mixing with other materials difficult.

[0004] Hydrophobic functional groups can also be introduced into the above water-soluble polymer by reacting with an allyl halide to perform allylation (see, for example, Patent Document 3). However, allyl halide has high reactivity, so most of the amino groups in the above water-soluble polymer are hydrophobized, which may result in loss of water solubility.

[0005] Japanese National Publication of International Patent Application No. 2022-500519, Japanese Unexamined Patent Application Publication No. 2012-36431, Japanese Unexamined Patent Application Publication No. 11-005821

[0006] In view of the above-mentioned prior art, the present invention aims to provide a modified water-soluble polymer and a method for producing the same, which is a water-soluble polymer having an amino group and is water-soluble, and which is compatible with hydrophobic compounds such as oils by introducing a hydrophobic functional group, and which can effectively suppress the increase in viscosity.

[0007] As a result of diligent research, the present inventors have found that when introducing hydrophobic functional groups by acylation of a water-soluble polymer having amino groups, further allylation by reacting it with an allyl halide can effectively suppress the increase in viscosity, and have completed the present invention. That is, the first invention of this application relates to a method for producing a modified water-soluble polymer, comprising: [1] a step (I) of reacting a polymer (A) having primary amino groups with a carboxylic acid (B), and a step (II) of reacting a polymer (A) having primary amino groups with an allyl halide (C), wherein in step (I), 2 to 30 mol% of the total primary and secondary amino groups of the polymer (A) having primary amino groups are acylated by the carboxylic acid (B), and in step (II), 20 to 70 mol% of the total primary and secondary amino groups of the polymer (A) having primary amino groups are allylated by the allyl halide (C).

[0008] Hereinafter, [2] to [5] and

[10] are all preferred embodiments or models of the first invention of this application. [2] A method for producing a modified water-soluble polymer according to [1], wherein the polymer (A) having a primary amino group is polyallylamine (A1) or polyalkyleneimine (A2). [3] A method for producing a modified water-soluble polymer according to [1] or [2], wherein the weight-average molecular weight Mw of the polymer (A) having a primary amino group is 1000 to 6000. [4] A method for producing a modified water-soluble polymer according to any one of [1] to [3], wherein the carboxylic acid (B) is a carboxylic acid having 2 to 13 carbon atoms per carboxyl group. [5] A method for producing a modified water-soluble polymer according to any one of [1] to [4], wherein a modified water-soluble polymer having a GPC-based weight-average molecular weight Mwc of 800 to 9000 is produced. A method for producing a lubricant, softener, surfactant, resin curing agent, or metal corrosion inhibitor, comprising the steps of: producing a modified water-soluble polymer by the manufacturing method described in any one of items [1] to [5]; and producing a lubricant, softener, surfactant, resin curing agent, or metal corrosion inhibitor using the modified water-soluble polymer obtained in the first step.

[0009] The second invention of this application relates to a modified water-soluble polymer having amino groups, wherein 2 to 30 mol% of the total amino groups are acylamino groups and 20 to 70 mol% of the total amino groups are allylamino groups.

[0010] Hereinafter, [7] to [9] and

[11] are all preferred embodiments or models of the second invention of this application. [7] A modified water-soluble polymer according to [6] having a polyallylamine skeleton or a polyalkyleneimine skeleton. [8] A modified water-soluble polymer according to [6] or [7], having a GPC-based weight-average molecular weight Mwc of 800 to 9000. [9] A modified water-soluble polymer according to any one of [6] to [8], wherein the acylamino group has an alkyl group having 1 to 12 carbon atoms.

[11] A lubricant, softener, surfactant, resin curing agent, or metal corrosion inhibitor containing a modified water-soluble polymer according to any one of [6] to [9].

[0011] The present invention provides a modified water-soluble polymer that possesses several practically valuable properties, such as being water-soluble due to the presence of amino groups, having compatibility with hydrophobic compounds such as oils due to the introduction of hydrophobic functional groups, and being easily mixed with other materials due to the suppression of viscosity increases, as well as a method for producing the same.

[0012] The first invention of this application is a method for producing a modified water-soluble polymer, comprising the steps of (I) reacting a polymer (A) having a primary amino group with a carboxylic acid (B), and (II) reacting the polymer (A) having a primary amino group with an allyl halide (C), wherein in step (I), 2 to 30 mol% of the total primary and secondary amino groups of the polymer (A) having a primary amino group are acylated by the carboxylic acid (B), and in step (II), 20 to 70 mol% of the total primary and secondary amino groups of the polymer (A) having a primary amino group are allylated by the allyl halide (C). That is, in the production method of the first invention of this application, a polymer (A) having a primary amino group, a carboxylic acid (B), and an allyl halide (C) are used as starting materials. Various starting materials will be described below.

[0013] Polymer having primary amino groups (A) The polymer having primary amino groups (A) used in the first invention of this application may be any polymer having at least one primary amino group per molecule, and there are no other particular restrictions. From the viewpoint of reactivity with carboxylic acids (B) and allyl halides (C), the polymer having primary amino groups (A) preferably has 2 to 110 primary amino groups per molecule, and more preferably has 10 to 90 primary amino groups per molecule. The polymer having primary amino groups (A) may or may not have functional groups other than primary amino groups, such as secondary amino groups, tertiary amino groups, quaternary amino groups, etc.

[0014] There are no particular restrictions on the skeleton of polymer (A) having a primary amino group. It can have one or more skeletons selected from various skeletons such as a carbon skeleton, silicon skeleton, oxygen skeleton, and sulfur skeleton, but it is preferable to have a carbon skeleton. If a carbon skeleton is present, the carbon skeleton may or may not have double and / or triple bonds, and may or may not have heteroatoms such as oxygen, nitrogen, and sulfur. The skeleton of polymer (A) having a primary amino group may be linear, branched, or cyclic.

[0015] As described above, the polymer (A) having primary amino groups preferably has 2 to 110 primary amino groups per molecule, and therefore it is preferable to have multiple constituent units having primary amino groups. It is particularly preferable to have multiple constituent units having primary amino groups that have the same structure, that is, it is particularly preferable to have repeating units having primary amino groups. Only one type of constituent unit having primary amino groups may be used, or two or more types may be used in combination. Examples of constituent units having primary amino groups (preferably repeating units) include constituent units derived from allylamines and constituent units derived from alkyleneimines. That is, the polymer (A) having primary amino groups preferably has a polyallylamine skeleton, a polyalkyleneimine skeleton, etc. Because it has the above-mentioned preferred skeleton, the polymer (A) having primary amino groups preferably is a polyallylamine (A1) or a polyalkyleneimine (A2).

[0016] The polymer (A) having primary amino groups may consist only of constituent units having primary amino groups, or it may also contain other constituent units. There are no particular restrictions on the proportion of constituent units having primary amino groups in the polymer (A) having primary amino groups, but it is preferably 7 mol% or more, more preferably 15 mol% or more, and particularly preferably 30 mol% or more.

[0017] Examples of constituent units other than those having a primary amino group include those derived from methylallylamine, dimethylallylamine, methoxycarbonylated allylamine, methylcarbonylated allylamine, ureated allylamine, diallylamine or its derivatives, acrylamide, anionic monomers such as monocarboxylic acids and dicarboxylic acids, and nonionic monomers such as acrylamide, sulfur dioxide, and styrene.

[0018] A polymer (A) having a primary amino group may also have a secondary amino group and / or a tertiary amino group in addition to the primary amino group, and it is preferable that it has a secondary amino group. For example, when polyallylamine (A1) is used as the polymer (A) having a primary amino group, a monomer having a secondary amino group and / or a tertiary amino group can be introduced into polyallylamine (A1) in addition to the primary amino group by introducing a monomer having a secondary amino group and / or a tertiary amino group as a copolymer component. Also, for example, when polyalkyleneimine (A2) is used as the polymer (A) having a primary amino group, a secondary amino group can be introduced into polyalkyleneimine (A2) by forming a structure in which the constituent units derived from the polyalkyleneimine are repeated in a linear manner, and a tertiary amino group can be introduced into polyalkyleneimine (A2) by forming a branched structure.

[0019] In polymer (A) having primary amino groups, there are no particular restrictions on the proportion of secondary and / or tertiary amino groups in addition to primary amino groups. The proportion can be set appropriately depending on the type, properties, and application of the target modified water-soluble polymer. However, from the viewpoint of water solubility, it is preferable that the total amount of primary and secondary amino groups is 0.5 moles or more, more preferably 0.6 moles or more, and particularly preferable 0.7 moles or more, per mole of total amino groups (total nitrogen atoms) in polymer (A) having primary amino groups. Furthermore, from the viewpoint of ease of reaction, it is preferable that the proportion of primary amino groups to 1 mole of total amino groups (total nitrogen atoms) in polymer (A) having primary amino groups is 0.07 moles or more, more preferably 0.15 moles or more, and particularly preferable 0.3 moles or more.

[0020] There are no particular restrictions on the molecular weight of the polymer (A) having a primary amino group. It can be set appropriately depending on the type, properties, and application of the target modified water-soluble polymer. However, the weight-average molecular weight (Mw) is preferably 1,000 to 6,000, more preferably 1,000 to 5,000, and particularly preferably 1,000 to 4,000.

[0021] (A1) Polyallylamine A polyallylamine (A1), which is a preferred example of the polymer (A) having a primary amino group used in the first invention of this application, is an allylamine (co)polymer having a structural unit derived from allylamine. Here, "allylamine (co)polymer" is a concept that encompasses both allylamine homopolymers and allylamine copolymers having structural units derived from allylamine and structural units derived from other monomers. That is, the polyallylamine (A1) used in this embodiment only needs to have structural units derived from allylamine, and may also be a copolymer having other structural units, or it may be a so-called homopolymer that does not have other structural units.

[0022] Constituent units derived from allylamine (A1) The constituent units derived from allylamine monomers, which are essential constituent units of polyallylamine, have the structure represented by the following formula (I).

[0023] Here, the constituent unit derived from the monoallylamine monomer only needs to have the structure represented by formula (I) above, and does not need to be a structure actually obtained by polymerizing monoallylamine. For example, it may be produced using an addition salt of monoallylamine as the starting monomer, and then the addition salt may be removed. The addition salt of monoallylamine used in this case is usually an inorganic salt of monoallylamine, and examples of such salts include monoallylamine hydrochloride, sulfate, phosphate, perchlorate, and nitrate, but it is preferable to use the hydrochloride due to its availability. Organic salts such as acetate can also be used.

[0024] Other structural units derived from allylamine: When the (A1) polyallylamine used in this embodiment is a copolymer, there are no particular restrictions on structural units other than those derived from monoallylamine. Such structural units can be derived by copolymerizing with monomers copolymerizable with monoallylamine as appropriate. Preferred copolymerizable monomers include, but are not limited to, monoallylamines such as methylallylamine and dimethylallylamine or their addition salts; diallylamines such as diallylamine and diallylmethylamine or their addition salts; diallyldialkylammonium salts such as diallyldimethylammonium chloride; acrylamides such as acrylamide, dimethylacrylamide, acryloylmorpholine, N-[3-(dimethylamino)propyl](meth)acrylamide, (3-acrylamidopropyl)trimethylammonium chloride, and (3-methacrylamidopropyl)trimethylammonium chloride; allyl alcohols, allyl ethers such as ethylene glycol monoallyl ether, unsaturated carboxylic acids such as (meth)acrylic acid (sodium) or their addition salts; unsaturated dicarboxylic acids such as maleic acid and fumaric acid or their salts; sulfur dioxide; allyl sulfonic acids such as (meth)allyl sulfonic acid (sodium) or their addition salts; vinyl sulfonic acids such as vinyl sulfonic acid (sodium) or their addition salts; sodium isoprene sulfonate, etc. Other monomers besides monoallylamine can be used individually or in combination of two or more.

[0025] There are no particular restrictions on the molecular weight of the (A1) polyallylamine used in this embodiment. A suitable (co)polymer with an appropriate molecular weight may be polymerized depending on the type, properties, and application of the target modified water-soluble polymer. From the viewpoint of water solubility and handling properties, a weight-average molecular weight (Mw) of 1,000 to 6,000 is preferred. A weight-average molecular weight (Mw) of 1,000 to 5,000 is more preferred, and 1,000 to 4,000 is particularly preferred. The weight-average molecular weight (Mw) of (A1) polyallylamine can be measured, for example, by gel permeation chromatography (GPC) using a liquid chromatograph. The molecular weight of (A1) polyallylamine can be appropriately adjusted by adjusting the presence, type and composition of comonomers, temperature, time and pressure in the polymerization process, and type and amount of radical initiator used in the polymerization process.

[0026] (A1) There are no particular restrictions on the intrinsic viscosity [η] of polyallylamine, and it can be set appropriately in relation to the required physical properties and applications. (A1) The viscosity of polyallylamine can also be adjusted appropriately by adjusting the presence, type and composition of comonomers, temperature, time and pressure in the polymerization process, and the type and amount of radical initiator used in the polymerization process.

[0027] (A1) There are no particular restrictions on the proportion of constituent units derived from allylamine in polyallylamine, but it is preferably 50 to 100 mol%, and more preferably 70 to 100 mol%. By having the proportion of constituent units derived from allylamine within the above range, desirable properties such as water solubility, handling properties, and low viscosity can be achieved more easily. The composition of (A1) polyallylamine, including the proportion of constituent units derived from allylamine, can be appropriately adjusted depending on the polymerization conditions, in particular the composition of the monomer supplied during polymerization.

[0028] (A2) Polyalkyleneimine (A2), which is a preferred example of the polymer (A) having a primary amino group used in the first invention of this application, has constituent units derived from alkyleneimine. More specifically, polyalkyleneimine (A2) has constituent units of the structure represented by the following formula (II). In the above formula (II), R １ R is an alkylene group, and there are no particular restrictions on the number of carbon atoms, but it is usually 2 to 5, preferably 2 to 4, and particularly preferably 2 to 3. １ The structure may be linear or branched, may contain heteroatoms such as oxygen and sulfur, and may be partially substituted. Although the structure represented by formula (II) above has a secondary amino group, the polyalkyleneimine (A2) used in this embodiment has, in addition to the structure represented by formula (II) above, the structure shown by formula (III) below at its terminal, thereby having a primary amino group. In the above formula (III), R ２ Each of these is an alkylene group, and there is no particular restriction on the number of carbon atoms, but it is usually 2 to 5, preferably 2 to 4, and particularly preferably 2 to 3. ２ It may be linear or branched, may contain heteroatoms such as oxygen and sulfur, and may be partially substituted.

[0029] Preferred specific examples of polyalkyleneimines (A2) include polyethyleneimine, polypropyleneimine, and ethylene oxide adducts of polyethyleneimine obtained by adding ethylene oxide while leaving at least one amidable amino group. Among these, polyethyleneimine is particularly preferred.

[0030] Polyethyleneimine is available in various forms with different degrees of branching and molecular weights. When producing the polyethyleneimine used in this embodiment, ethyleneimine can be used as a raw material. However, when ethyleneimine is polymerized, it does not usually result in a polymer with a completely linear structure. Instead, a polyethyleneimine is obtained that has a degree of branching that depends on the manufacturing conditions such as acid concentration and polymerization temperature, and that has tertiary amino groups in addition to primary and secondary amino groups. An example of the structure of polyethyleneimine as described above is shown in formula (IV) below.

[0031] There are no particular restrictions on the molecular weight of polyethyleneimine, but its weight-average molecular weight Mw is preferably 1000 to 6000, more preferably 1000 to 5000, and most preferably 1000 to 4000.

[0032] Polyethyleneimine can be synthesized, for example, by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst. Alternatively, commercially available polyethyleneimines, such as Lupasol (product names: Lupasol SK (average molecular weight approximately 2,000,000), Lupasol G20 (average molecular weight approximately 1,300), Lupasol G20 WF (average molecular weight approximately 1,300), Lupasol P (average molecular weight approximately 750,000), Lupasol PS (average molecular weight approximately 750,000), Lupasol PR 8515 (2,000), Lupasol PN 40, Lupasol WF (average molecular weight approximately 25,000), Lupasol SC-61B (average molecular weight 110,000) and Lupasol) from BASF. You can also use FG), Epomin (model numbers: SP-003 (average molecular weight approximately 300), SP-006 (average molecular weight approximately 600), SP-012 (average molecular weight approximately 1,200), SP-018 (average molecular weight approximately 1,800), SP-200 (average molecular weight approximately 10,000), and P-1000 (average molecular weight approximately 70,000)) commercially available from Nippon Shokubai Co., Ltd., and BPEI (distributor code 161-17831 (average molecular weight approximately 600), distributor code 167-17811 (average molecular weight approximately 1,800), and distributor code 164-17821 (average molecular weight approximately 10,000)) commercially available from Wako Pure Chemical Industries, Ltd.

[0033] (B) Carboxylic acid The carboxylic acid (B) used in the present invention is a compound having a carboxyl group that can react with a polymer (A) having a primary amino group, and there are no other particular restrictions, but examples of suitable carboxylic acids (B) are listed below as (B1) and (B2).

[0034] (B1) Long-chain, linear or branched carboxylic acids having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms in an alkyl or alkenyl group, such as caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and mixtures thereof, preferably lauric acid, stearic acid, palmitic acid and oleic acid.

[0035] Among the above (B) carboxylic acids, saturated monocarboxylic acids (acetic acid, propionic acid, capric acid, lauric acid, stearic acid, behenic acid, etc.), unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, oleic acid, etc.), aliphatic oxycarboxylic acids (glycolic acid, lactic acid, gluconic acid, etc.), aliphatic polycarboxylic acids (oxalic acid, succinic acid, adipic acid, azelaic acid, sebatic acid, maleic acid, fumaric acid, itaconic acid, etc.), aromatic carboxylic acids (phthalic acid, trimellitic acid, pyromellitic acid, etc.) are preferred, carboxylic acids with 2 to 13 carbon atoms per carboxyl group are more preferred, and carboxylic acids with 8 to 12 carbon atoms per carboxyl group are particularly preferred. (B) Carboxylic acid may be used alone or in combination of two or more types.

[0036] (C) Allyl Halide The allyl halide (C) used in the present invention has a structure represented by the following general formula (V). In the above formula (V), X represents a halogen atom. Preferred halogen atoms include chlorine, bromine, and iodine. Preferred specific examples of allyl halide (C) include allyl chloride, allyl bromide, and allyl iodide.

[0037] Step (I) The method for producing a modified water-soluble polymer according to the first invention of this application comprises step (I) of reacting a polymer (A) having a primary amino group with a carboxylic acid (B). In step (I), by reacting the polymer (A) having a primary amino group with the carboxylic acid (B), the primary amino group in polymer (A) is acylated, and an acylamino group is formed.

[0038] In step (I), 2 to 30 mol% of the primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) of the polymer (A) having primary amino groups are acylated with a carboxylic acid (B).

[0039] By acylating 2 mol% or more of the primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) of a polymer (A) having primary amino groups, sufficient hydrophobic groups are introduced, and compatibility with hydrophobic compounds such as oils can be imparted to the polymer (A) having primary amino groups, which is inherently hydrophilic or water-soluble. Preferably, 2 mol% or more of the primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) of a polymer (A) having primary amino groups are acylated with a carboxylic acid (B), and more preferably, 4 mol% or more are acylated with a carboxylic acid (B).

[0040] When the proportion of acylated primary amino groups of the polymer (A) having primary amino groups (the total of primary amino groups and secondary amino groups when the polymer (A) having primary amino groups also has secondary amino groups) is 30 mol% or less, the formation of highly polar amide groups is suppressed to a certain extent, and an excessive increase in viscosity can be suppressed. The proportion of acylated primary amino groups of the polymer (A) having primary amino groups (the total of primary amino groups and secondary amino groups when the polymer (A) having primary amino groups also has secondary amino groups) is preferably 80 mol% or less, more preferably 70 mol% or less.

[0041] In the step (I), the reactivity between the primary amino groups of the polymer (A) (primary amino groups and secondary amino groups when the polymer (A) having primary amino groups also has secondary amino groups) and the carboxylic acid (B) is generally good. Therefore, the proportion of acylated primary amino groups (the total of primary amino groups and secondary amino groups when the polymer (A) having primary amino groups also has secondary amino groups) usually matches the value calculated from the total number of moles of primary amino groups (the total of primary amino groups and secondary amino groups when the polymer (A) having primary amino groups also has secondary amino groups) of the polymer (A) subjected to the reaction and the number of moles of the carboxylic acid (B). Therefore, the proportion can be calculated with relatively high accuracy from the amounts and chemical structures of the polymer (A) and the carboxylic acid (B) subjected to the reaction. Experimentally, the proportion of primary amino groups of the polymer (A) having primary amino groups (the total of primary amino groups and secondary amino groups when the polymer (A) having primary amino groups also has secondary amino groups) acylated in the step (I) can be measured by identifying the structure of constituent components via any one or a combination of potentiometric titration, solid content measurement, nuclear magnetic resonance spectrum measurement, infrared absorption spectrum measurement, gas chromatography measurement, and gas chromatography-mass spectrometry measurement, and performing quantitative analysis by the calibration curve method.

[0042] Among the primary amino groups of the polymer (A) having a primary amino group (the total of primary amino groups and secondary amino groups when the polymer (A) having a primary amino group also has a secondary amino group), the proportion of those acylated in step (I) can be appropriately adjusted by methods conventionally used in the art. For example, it can be appropriately adjusted by adjusting the types and amounts of the polymer (A) and carboxylic acid (B) subjected to the reaction in step (I), the presence, types and amounts of components other than the polymer (A) and carboxylic acid (B) to be subjected to step (I), and the conditions of step (I) such as temperature, time, etc.

[0043] In step (I), the polymer (A) having a primary amino group and the carboxylic acid (B) can be reacted by directly bringing them into contact, mixing them, or the like. In step (I), only the polymer (A) having a primary amino group and the carboxylic acid (B) may be used, but a solvent or the like may further be used from the viewpoint of handling properties and the like. There is no particular limitation on the amount of carboxylic acid (B) used in step (I), but it is preferably 0.02 to 0.23 mol, more preferably 0.02 to 0.20 mol, particularly preferably 0.04 to 0.20 mol, per 1 mol of all amino groups (all nitrogen atoms) in the polymer (A) having a primary amino group.

[0044] There is no particular limitation on the temperature in step (I), but from the viewpoint of reactivity and the like, it is preferably 100 to 150°C, more preferably 100 to 140°C, particularly preferably 110 to 140°C. There is no particular limitation on the reaction time in step (I) either, but from the viewpoint of suppressing oxidative degradation of amines and the like, it is preferably 12 to 72 hours, more preferably 12 to 48 hours, particularly preferably 18 to 36 hours.

[0045] Step (II) The method for producing a modified water-soluble polymer according to the first invention of this application comprises step (II) of reacting a polymer (A) having a primary amino group with an allyl halide (C). In step (II), by reacting the polymer (A) having a primary amino group with the allyl halide (C), the primary amino group in polymer (A) is preferably allylated, and an allylamino group is formed.

[0046] In step (II), 20 to 70 mol% of the primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) of the polymer (A) having primary amino groups are allylated with allyl halide (C).

[0047] By allylation of 20 mol% or more of the primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups), the viscosity increase that may occur due to acylation in step (I) can be effectively suppressed. Preferably, 20 mol% or more of the primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) of the polymer (A) having primary amino groups are allylated with allyl halide (C), and more preferably, 25 mol% or more are allylated with allyl halide (C).

[0048] By ensuring that the proportion of primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) that are allylated in polymer (A) having primary amino groups is 70 mol% or less, the decrease in water solubility and hydrophilicity due to the excessive introduction of hydrophobic groups can be effectively suppressed. The proportion of primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) that are allylated in step (II) in polymer (A) having primary amino groups is preferably 80 mol% or less, and more preferably 70 mol% or less.

[0049] In step (II), the reactivity between the primary amino groups of polymer (A) (or the primary and secondary amino groups if polymer (A) having primary amino groups also has secondary amino groups) and allyl halide (C) is usually good. Therefore, the proportion of allylated primary amino groups (or the sum of primary and secondary amino groups if polymer (A) having primary amino groups also has secondary amino groups) usually matches the value calculated from the number of moles of primary amino groups (or the sum of primary and secondary amino groups if polymer (A) having primary amino groups also has secondary amino groups) and the number of moles of allyl halide (C) used in the reaction. Thus, it can be determined with relatively high accuracy from the amount and structure of polymer (A) and allyl halide (C) used in the reaction. Furthermore, the proportion of primary amino groups (or the total of primary and secondary amino groups if polymer (A) also has secondary amino groups) that are allylated in step (II) of polymer (A) having primary amino groups can be experimentally determined by identifying the structure of the constituent components using one or a combination of potentiometric titration, solid content measurement, nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, gas chromatography, and gas chromatography-mass spectroscopy, as well as quantitative analysis using a calibration curve.

[0050] The proportion of primary amino groups (or the total of primary and secondary amino groups if the polymer (A) also has secondary amino groups) that are allylated in step (II) of the polymer (A) having primary amino groups can be appropriately adjusted by methods conventionally used in the art. For example, this can be appropriately adjusted by adjusting the type and amount of polymer (A) and allyl halide (C) subjected to the reaction in step (II), the presence, type and amount of other components subjected to step (II), temperature, time, and other conditions of step (II).

[0051] In step (II), the polymer (A) having primary amino groups and the allyl halide (C) can be reacted by directly contacting or mixing them. In step (II), only the polymer (A) having primary amino groups and the allyl halide (C) may be used, but a solvent, catalyst, etc. may also be used from the viewpoint of promoting the reaction. There are no particular restrictions on the amount of allyl halide (C) used in step (II), but it is preferable to use 0.1 to 0.6 moles, more preferably 0.2 to 0.55 moles, and particularly preferable 0.25 to 0.55 moles, per mole of total amino groups (total nitrogen atoms) in the polymer (A) having primary amino groups.

[0052] There are no particular restrictions on the temperature in step (II), but from the viewpoint of reactivity and suppression of allyl halide volatilization, it is preferably 30 to 50°C, more preferably 30 to 45°C, and particularly preferably 35 to 45°C. There are no particular restrictions on the reaction time in step (II), but from the viewpoint of suppressing oxidative degradation of the amine, it is preferably 12 to 48 hours, more preferably 12 to 36 hours, and particularly preferably 18 to 36 hours.

[0053] By carrying out step (II), the increase in viscosity that may occur or has occurred due to acylation in step (I) can be effectively suppressed. For example, the viscosity of the modified water-soluble polymer after step (II) is preferably lower than the viscosity before step (II) after step (I), more preferably 95% or less of the viscosity before step (II) after step (I), and particularly preferably 70% or less. Furthermore, the viscosity of the modified water-soluble polymer after step (II) is preferably 20 mPa·s or less, more preferably 15 mPa·s or less, and particularly preferably 10 mPa·s or less.

[0054] Method for producing a modified water-soluble polymer The method for producing a modified water-soluble polymer according to the first invention of this application comprises a step (I) of reacting a polymer (A) having a primary amino group with a carboxylic acid (B), and a step (II) of reacting a polymer (A) having a primary amino group with an allyl halide (C). Therefore, the method for producing a modified water-soluble polymer according to the first invention of this application may consist only of steps (I) and (II), or it may include steps (I) and (II) plus other steps.

[0055] There are no particular restrictions on the other steps other than steps (I) and (II), and for example, steps that have been conventionally applied in the art to the production of modified water-soluble polymers can be appropriately adopted. For example, steps for producing, preparing, or purifying a polymer (A) having a primary amino group, a carboxylic acid (B), or an allyl halide (C), or steps for recovering, purifying, drying, or further modifying the produced modified water-soluble polymer can be appropriately adopted.

[0056] There are no particular restrictions on the order in which steps (I) and (II) are carried out. Step (II) may be carried out after step (I), or step (I) may be carried out after step (II), or steps (I) and (II) may be carried out simultaneously. Since the reaction temperature of step (I) is often higher than that of step (II), it is preferable to carry out step (II) after step (I) from the viewpoint of preventing the structure of the allylated amine produced in step (II) from decomposing at a higher temperature.

[0057] The second invention of this application is a modified water-soluble polymer having amino groups, wherein 2 to 30 mol% of the total amino groups are acylamino groups and 20 to 70 mol% of the total amino groups are allylamino groups. Therefore, the modified water-soluble polymer of the second invention of this application has a polymer backbone and amino groups, and has acylamino groups and allylamino groups each accounting for a predetermined proportion of the amino groups.

[0058] Polymer Skeleton There are no particular restrictions on the polymer skeleton constituting the modified water-soluble polymer of the second invention of this application. One or more skeletons can be selected from various skeletons such as carbon skeletons, silicon skeletons, oxygen skeletons, and sulfur skeletons, but it is preferable that at least a part of it is a carbon skeleton. In the case of a carbon skeleton, the carbon skeleton may or may not have double bonds and / or triple bonds, and may or may not have heteroatoms such as oxygen, nitrogen, and sulfur. The polymer skeleton constituting the modified water-soluble polymer of the second invention of this application may be linear, branched, or cyclic. Details of the polymer skeleton constituting the modified water-soluble polymer of the second invention of this application are the same as those described above in relation to polymer (A) used in the first invention of this application.

[0059] The polymer skeleton constituting the modified water-soluble polymer of the second invention of this application preferably has a polyallylamine skeleton or a polyalkyleneimine skeleton. Having a polyallylamine skeleton or a polyalkyleneimine skeleton allows for the introduction of desired functional groups, such as primary amino groups and other primary amino groups, with a high degree of freedom. Furthermore, by introducing primary amino groups, acylamino groups and allylamino groups can also be introduced with a high degree of freedom. The polyallylamine skeleton and the polyalkyleneimine skeleton are also preferable from the viewpoint of hydrophilicity and water solubility. Details of the polyallylamine skeleton and the polyalkyleneimine skeleton preferably used in the modified water-soluble polymer of the second invention of this application are the same as those described above in relation to the polyallylamine (A1) and polyalkyleneimine (A2) in the preferred embodiment of the first invention of this application.

[0060] There are no particular restrictions on the amount of amino groups in the modified water-soluble polymer of the second basic invention of the amino acid, but it is preferable to have 20 to 110 amino groups per molecule, and more preferably 25 to 90 amino groups per molecule. Here, "amino group" is a concept that includes acylamino groups and allylamino groups, and the above number of amino groups per molecule is the sum of the number of amino groups that are neither acylated nor allylated, acylamino groups, and allylamino groups.

[0061] The modified water-soluble polymer of the second invention of this application can preferably be manufactured by using a water-soluble polymer having primary amino groups as a raw material, acyling a portion of the primary amino groups to form acylamino groups, and allylating another portion of the primary amino groups to form allylamino groups. More preferably, it can be manufactured by the manufacturing method of the first invention of this application. In this case, some of the primary amino groups may remain in the modified water-soluble polymer of the second invention of this application without being acyled or allylated, or all of the primary amino groups may be acyled or allylated, resulting in the absence of primary amino groups. Therefore, there is no particular limit to the amount of primary amino groups in the modified water-soluble polymer of the second invention of this application, but it is preferable that there be 2 to 110 primary amino groups per molecule, and more preferably that there be 10 to 90 primary amino groups per molecule.

[0062] The modified water-soluble polymer of the second invention of the basic application for acylamino has acylamino groups, and 2 to 30 mol% of the total amino groups of the modified water-soluble polymer are composed of acylamino groups. By having 2 mol% or more of the total amino groups composed of acylamino groups, sufficient hydrophobic groups are introduced, and compatibility with hydrophobic compounds such as oils can be imparted to the modified water-soluble polymer of the second invention of this application. Preferably, 3 mol% or more of the total amino groups of the modified water-soluble polymer of the second invention of this application are composed of acylamino groups, and more preferably 4 mol% or more are composed of acylamino groups.

[0063] By having a ratio of acylamino groups to the total amino groups of the modified water-soluble polymer of the second invention of this application of 30 mol% or less, the formation of highly polar amide groups and the like can be suppressed to some extent, thereby suppressing an excessive increase in viscosity. Preferably, the ratio of acylamino groups to the total amino groups of the modified water-soluble polymer of the second invention of this application is 23 mol% or less, and more preferably 20 mol% or less. The ratio of acylamino groups to the total amino groups of the modified water-soluble polymer can be measured by identifying the structure of the constituent components by any or a combination of potentiometric titration, solid content measurement, nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, gas chromatography, and gas chromatography-mass spectroscopy, as well as by performing quantitative analysis using a calibration curve method.

[0064] The proportion of acylamino groups to the total amino groups in the modified water-soluble polymer of the second invention of this application can be appropriately adjusted using methods conventionally used in the art. For example, it can be appropriately adjusted by adjusting the type and amount of raw material polymers, acylation agents such as carboxylic acids, the presence, type and amount of other components used in the manufacturing process, and manufacturing conditions such as temperature and time.

[0065] The acylamino group constituting the modified water-soluble polymer of the second invention of this application preferably has a structure derived from a primary amino group and a carboxylic acid. Details of the carboxylic acid used here and its preferred embodiments are the same as those described above in relation to carboxylic acid (B). As described above, in the acylation step, a carboxylic acid having 2 to 13 carbon atoms per carboxyl group can preferably be used, in which case the acylamino group will have an alkyl group having 1 to 12 carbon atoms. It is more preferable that the acylamino group has an alkyl group having 7 to 13 carbon atoms.

[0066] The modified water-soluble polymer of the second invention of the basic application for allylamino has allylamino groups, and 20 to 70 mol% of the total amino groups of the modified water-soluble polymer are composed of allylamino groups. By having 20 mol% or more of the total amino groups composed of allylamino groups, the increase in viscosity that may be generated or has been generated by the acylamino groups can be effectively suppressed. Preferably, the modified water-soluble polymer of the second invention of this application has 25 mol% or more of the total amino groups composed of allylamino groups, and more preferably 30 mol% or more of the total amino groups composed of allylamino groups.

[0067] By having allylamino groups in the total amino groups of the modified water-soluble polymer of the second invention of this application be 70 mol% or less, the decrease in water solubility and hydrophilicity due to the excessive introduction of hydrophobic groups can be effectively suppressed. Preferably, the proportion of allylamino groups in the total amino groups of the modified water-soluble polymer of the second invention of this application is 60 mol% or less, and more preferably 50 mol% or less. The proportion of allylamino groups in the total amino groups of the modified water-soluble polymer can be measured by identifying the structure of the constituent components by any or a combination of potentiometric titration, solid content measurement, nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, gas chromatography, and gas chromatography-mass spectroscopy, as well as by performing quantitative analysis using a calibration curve method.

[0068] The proportion of allylamino groups to the total amino groups in the modified water-soluble polymer of the second invention of this application can be appropriately adjusted using methods conventionally used in the art. For example, it can be appropriately adjusted by adjusting the type and amount of raw material polymers, allyl halides and other allylating agents, the presence, type and amount of other components used in the manufacturing process, and manufacturing conditions such as temperature and time.

[0069] The allylamino group constituting the modified water-soluble polymer of the second invention of this application preferably has a structure derived from a primary amino group and an allyl halide. The details of the allyl halide used herein and its preferred embodiments are the same as those described above in relation to allyl halide (C).

[0070] Modified Water-Soluble Polymer There are no particular restrictions on the molecular weight of the modified water-soluble polymer of the second invention of this application. It can be set appropriately according to the type, physical properties, and application of the modified water-soluble polymer. However, the weight-average molecular weight (Mwc) in terms of polyethylene glycol by the GPC method is preferably 800 to 9000, more preferably 800 to 5000, and particularly preferably 850 to 3000. The molecular weight of the modified water-soluble polymer of the second invention of this application can be appropriately adjusted by methods conventionally known in the art. For example, it can be appropriately adjusted by adjusting the molecular weight of the water-soluble polymer used as a raw material, the type and / or molecular weight of the acylating agent and / or allylating agent also used as a raw material, and the degree of acylating and / or allylating.

[0071] The GPC-based weight-average molecular weight of polyethylene glycol (hereinafter sometimes abbreviated as "Mwc") is one method of calculating weight-average molecular weight using gel permission chromatography. A calibration curve is created from the measurement results of polyethylene glycol with a known molecular weight, and the molecular weight is calculated based on that calibration curve. The obtained molecular weight is not an absolute value, but a relative value of the molecular size of polyethylene glycol in the eluent and the substance being measured. As described later, since Mwc is obtained by GPC measurement in an aqueous solution, in the case of a modified water-soluble polymer having both hydrophobic and hydrophilic structural parts, such as the modified water-soluble polymer of the second invention of this application, there is a tendency to observe a smaller actual molecular weight (presumably because it takes a shape that hides the hydrophobic structural part within the molecule). Also, the greater the branching, the more likely it is that a smaller molecular weight will be observed. For this reason, for example, it cannot necessarily be directly compared with the weight-average molecular weight Mw of the polymer (A) having a primary amino group as described above.

[0072] More specifically, the GPC-based weight-average molecular weight (Mw) of polyethylene glycol can be measured using gel permeation chromatography (GPC) with a high-performance liquid chromatograph. For example, a sample can be adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl of this sample can be used. The eluent can be 0.300 mol / L 2-aminoethanol and 0.305 mol / L aqueous hydrogen chloride solution, and the procedure can be performed at a column temperature of 30°C and a flow rate of 1.0 ml / min. Calibration curves can be obtained using polyethylene glycols with molecular weights of 106, 410, 610, 1010, 1450, 3860, 8160, 16100, 22160, 48290, 66200, 117900, 272400, and 545000 as standard samples, and the GPC-based weight-average molecular weight (Mw) of polyethylene glycol can be determined based on these calibration curves.

[0073] The modified water-soluble polymer of the second invention of this application, by having a predetermined amount of allylamino groups, can effectively suppress the increase in viscosity that may occur or has occurred due to acylamino groups. For example, the viscosity of the modified water-soluble polymer of the second invention of this application is preferably lower than that of a modified water-soluble polymer having the same structure except that it does not have allylamino groups and has primary amino groups instead of allylamino groups, more preferably 100% or less of the viscosity of a modified water-soluble polymer having the same structure except that it has primary amino groups instead of allylamino groups, and particularly preferably 95% or less. Furthermore, the viscosity of the modified water-soluble polymer of the second invention of this application is preferably 20 mPa·s or less, more preferably 15 mPa·s or less, and particularly preferably 10 mPa·s or less.

[0074] There are no particular limitations on the method for producing the modified water-soluble polymer of the second invention of this application, but it is preferable to produce it using the method of the first invention of this application. The method of the first invention of this application can also be used to produce water-soluble polymers other than the modified water-soluble polymer of the second invention of this application, but it is particularly suitable for producing the modified water-soluble polymer of the second invention of this application.

[0075] Applications The modified water-soluble polymer produced by the manufacturing method of the first invention of this application, and the modified water-soluble polymer of the second invention of this application (hereinafter collectively referred to as "the modified water-soluble polymer of the present invention") are water-soluble due to the presence of amino groups, and also possess compatibility with hydrophobic compounds such as oils due to the introduction of hydrophobic functional groups. Furthermore, the increase in viscosity is suppressed, making it easy to mix with other materials, thus having high practical value. Taking advantage of the above-mentioned excellent properties, the modified water-soluble polymer of the present invention can be suitably used in various applications such as lubricants, softeners, surfactants, resin curing agents, and metal corrosion inhibitors.

[0076] The present invention will be described in more detail below with reference to the examples. However, the scope of the present invention is not limited in any way by these examples.

[0077] The physical properties and characteristics of the examples / comparative examples were evaluated by the following method. [Water solubility] The modified water-soluble polymers produced in the examples / comparative examples were left to stand for 24 hours after the reaction was complete, and the presence or absence of solid formation and precipitation was visually checked and evaluated according to the following criteria. ○: No solid or precipitate was formed. ×: Solid or precipitate was formed.

[0078] [Viscosity] A 15% aqueous solution of the modified water-soluble polymer produced in the Examples / Comparative Examples was prepared, and the viscosity of the aqueous solution was measured using a Brookfield viscometer (manufactured by Eiko Seiki Co., Ltd., model number: DV3T).

[0079] [Weight-average molecular weight (Mwc) of polyethylene glycol by GPC method] The molecular weight was measured by gel permeation chromatography (GPC) using a high-performance liquid chromatograph manufactured by JASCO (Japan Spectroscopic Co., Ltd.). The sample was adjusted to a concentration of 0.5 g / 100 ml with the eluent, and 20 μl was used. The eluents used were 0.300 mol / L 2-aminoethanol and 0.305 mol / L aqueous hydrogen chloride solution. The column temperature was 30°C and the flow rate was 1.0 ml / min. Calibration curves were obtained using polyethylene glycols with molecular weights of 106, 410, 610, 1010, 1450, 3860, 8160, 16100, 22160, 48290, 66200, 117900, 272400, and 545000 as standard samples, and the weight-average molecular weight (Mwc) of polyethylene glycol by GPC method was determined based on these calibration curves.

[0080] The materials and raw materials used in the examples / comparative examples are as follows: (A) Polymers having primary amino groups (A1) Polyethyleneimine 1 Lupasol PR 8515 (manufactured by BASF) Weight-average molecular weight: 2000 Primary amino group / Secondary amino group / Tertiary amino group (molar ratio) = 1 / 0.9 / 0.6 (A2) Polyallylamine 1 PAA-05 (manufactured by Nitto Boseki Co., Ltd.) Allylamine (free) homopolymer weight-average molecular weight: 5000 (A3) Polyallylamine 2 PAA-01 (manufactured by Nitto Boseki Co., Ltd.) Allylamine (free) homopolymer weight-average molecular weight: 1600 (A4) Polyallylamine 3 PAA-03 (manufactured by Nitto Boseki Co., Ltd.) Allylamine (free) homopolymer weight-average molecular weight: 3000 (A5) Polyallylamine 4 PAA-AC5050A (manufactured by Nitto Boseki Co., Ltd.) Partially amidated allylamine acetate polymer Weight-average molecular weight: 15,000 Number of carbon chains: 2 Amidation modification rate: 57% (A') Polydiallylamine 1 PAS-21 (manufactured by Nitto Boseki Co., Ltd.) Diallylamine homopolymer Weight-average molecular weight: 5,000

[0081] (B) Carboxylic Acids (B1) Dodecanoic acid (manufactured by Tokyo Chemical Industries, Ltd.) (12 carbon atoms per carboxyl group) (B2) Octanoic acid (manufactured by Tokyo Chemical Industries, Ltd.) (8 carbon atoms per carboxyl group) (B3) Acetic acid (manufactured by Nacalai Tesque Co., Ltd.) (2 carbon atoms per carboxyl group) (B4) Acetic anhydride (manufactured by Nacalai Tesque Co., Ltd.) (2 carbon atoms per carboxyl group)

[0082] (C) Allyl halide (C1) Allyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0083] (Comparative Example 2) Using (A1) polyethyleneimine 1 and (B1) dodecanoic acid, the mixture was heated at a temperature of 130°C to 140°C for 24 hours, and then the disappearance of the carboxylic acid was confirmed using a potentiometric automatic titrator (manufactured by Kyoto Electronics Manufacturing Co., Ltd., model number: AT-710) to produce a modified water-soluble polymer. The water solubility and viscosity of the obtained modified water-soluble polymer were evaluated according to the above method, and the results are shown in Table 1.

[0084] (Example 1) The modified water-soluble polymer obtained in Comparative Example 2 was adjusted to a concentration of 15% using water, and then (C1) allyl chloride was added dropwise to the aqueous solution of the modified water-soluble polymer heated to 40°C and reacted for 24 hours. After that, the disappearance of the peak derived from allyl chloride was confirmed by gas chromatography (Shimadzu Corporation, model number: GC-2030), and a modified water-soluble polymer was produced. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC) were evaluated according to the above method, and the results are shown in Table 1.

[0085] (Examples 2, 3 and 11, Comparative Example 3) Modified water-soluble polymers were produced in the same manner as in Example 1, except that the amount of allyl chloride used (C1) was changed to that shown in Table 1. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC) were evaluated according to the above method, and the results are shown in Table 1.

[0086] (Examples 4, Comparative Examples 1 and 4) (B1) Modified water-soluble polymers were produced in the same manner as in Example 1, except that dodecanoic acid was not used or the amount used was changed to those shown in Table 1. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC method) were evaluated according to the above method and the results are shown in Table 1.

[0087] (Example 5) A modified water-soluble polymer was produced in the same manner as in Example 1, except that (B2) octanoic acid was used instead of (B1) dodecanoic acid, and the amount used was changed as shown in Table 1. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC) were evaluated according to the above method, and the results are shown in Table 1.

[0088] (Example 6) A modified water-soluble polymer was produced in the same manner as in Example 1, except that (B3) acetic acid was used instead of (B1) dodecanoic acid. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC) were evaluated according to the above method, and the results are shown in Table 1.

[0089] (Example 7) A modified water-soluble polymer was produced in the same manner as in Example 5, except that (A2) polyallylamine 1 was used after removing water in a rotary evaporator instead of (A1) polyethyleneimine 1, and (B2) the amount of octanoic acid used was changed to that shown in Table 1. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC) were evaluated according to the above method and the results are shown in Table 1.

[0090] (Example 8) A modified water-soluble polymer was produced in the same manner as in Example 6, except that (A1) polyallylamine 1 was used after removing water in a rotary evaporator, (B4) acetic anhydride was used in the amount shown in Table 1 instead of acetic acid, and the reaction was carried out at a reaction temperature between 20°C and 30°C for 24 hours. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC) were evaluated according to the above method and the results are shown in Table 1.

[0091] (Example 9) A modified water-soluble polymer was produced in the same manner as in Example 6, except that (A1) polyethyleneimine 1 was replaced with (A3) polyallylamine 2 after the water was removed by distillation in a rotary evaporator, (B3) acetic acid was replaced with (B4) acetic anhydride, and the modification rate was calculated from the amount of unamidated amine remaining after the reaction was carried out at a reaction temperature of 20°C to 30°C for 24 hours using a potentiometric automatic titrator (manufactured by Kyoto Electronics Manufacturing Co., Ltd., model number: AT-710). The water solubility, viscosity, and weight-average molecular weight Mwc in terms of polyethylene glycol by GPC method were evaluated according to the above method and the results are shown in Table 1.

[0092] (Example 10) A modified water-soluble polymer was produced in the same manner as in Example 1, except that (A4) polyallylamine 3 was used after removing water in a rotary evaporator instead of (A1) polyethyleneimine 1, and the amount of (B1) dodecanoic acid used was changed to that shown in Table 1. The water solubility, viscosity, and weight-average molecular weight Mwc (equivalent to polyethylene glycol by GPC) were evaluated according to the above method and the results are shown in Table 1.

[0093] (Comparative Example 5) A modified water-soluble polymer was produced in the same manner as in Example 1, except that (A') polydiallylamine 1 was used after removing water in a rotary evaporator, instead of (A1) polyethyleneimine 1. The results of evaluating water solubility and viscosity according to the above method are shown in Table 1.

[0094] (Comparative Examples 6 to 11) Modified water-soluble polymers were produced in the same manner as in Examples 5 to 10, except that (C1) modification with allyl chloride was not performed. The results of evaluating water solubility and viscosity according to the above method are shown in Table 1.

[0095] (Comparative Example 12) (A5) Polyallylamine 4 was neutralized with a 25% sodium hydroxide aqueous solution and then desalted to obtain a modified water-soluble polymer. The water solubility and viscosity were evaluated according to the above method, and the results are shown in Table 1.

[0096] (Comparative Example 13) The modified water-soluble polymer obtained in Comparative Example 12 was adjusted to a concentration of 15% using water, and then the amount of (C1) allyl chloride listed in Table 1 was added dropwise to the modified water-soluble polymer aqueous solution heated to 40°C to produce a modified water-soluble polymer. The results of evaluating the water solubility and viscosity according to the above method are shown in Table 1.

[0097] (Comparative Example 14) A modified water-soluble polymer was produced in the same manner as in Comparative Example 6, except that (B2) octanoic acid was used instead of (B3) acetic acid, and the amount used was changed to that shown in Table 1. The results of evaluating the water solubility and viscosity according to the above method are shown in Table 1.

[0098]

[0099]

[0100] The modified water-soluble polymer and its manufacturing method of the present invention possess several practically valuable properties, such as being water-soluble due to the presence of amino groups, having compatibility with hydrophobic compounds such as oils due to the introduction of hydrophobic functional groups, and being easy to mix with other materials due to the suppression of viscosity increase. Therefore, it is possible to provide a modified water-soluble polymer that combines these properties, making it suitable for various applications such as lubricants, softeners, surfactants, resin curing agents, and metal corrosion inhibitors, and has high applicability in various fields of industry such as the machinery industry, chemical industry, and electrical and electronic industry.

Claims

1. A method for producing a modified water-soluble polymer, comprising the steps of (I) reacting a polymer (A) having primary amino groups with a carboxylic acid (B), and (II) reacting the polymer (A) having primary amino groups with an allyl halide (C), wherein in step (I), 2 to 30 mol% of the total primary and secondary amino groups of the polymer (A) having primary amino groups are acylated by the carboxylic acid (B), and in step (II), 20 to 70 mol% of the total primary and secondary amino groups of the polymer (A) having primary amino groups are allylated by the allyl halide (C).

2. The method for producing a modified water-soluble polymer according to claim 1, wherein the polymer (A) having a primary amino group is polyallylamine (A1) or polyalkyleneimine (A2).

3. A method for producing a modified water-soluble polymer according to claim 1 or 2, wherein the weight-average molecular weight Mw of the polymer (A) having a primary amino group is 1,000 to 6,000.

4. The method for producing a modified water-soluble polymer according to claim 1 or 2, wherein the carboxylic acid (B) is a carboxylic acid having 2 to 13 carbon atoms per carboxyl group.

5. A method for producing a modified water-soluble polymer according to claim 1 or 2, wherein a modified water-soluble polymer having a GPC-based weight-average molecular weight Mwc of 800 to 9000 is produced.

6. A modified water-soluble polymer having amino groups, wherein 2 to 30 mol% of the total amino groups are acylamino groups and 20 to 70 mol% of the total amino groups are allylamino groups.

7. The modified water-soluble polymer according to claim 6, having a polyallylamine skeleton or a polyalkyleneimine skeleton.

8. The modified water-soluble polymer according to claim 6 or 7, wherein the weight-average molecular weight Mwc, calculated using the GPC method for polyethylene glycol, is 800 to 9000.

9. The modified water-soluble polymer according to claim 6 or 7, wherein the acylamino group has an alkyl group having 1 to 12 carbon atoms.

10. A method for producing a lubricant, softener, surfactant, resin curing agent, or metal corrosion inhibitor, comprising the steps of: producing a modified water-soluble polymer by the manufacturing method described in claim 1 or 2; and producing a lubricant, softener, surfactant, resin curing agent, or metal corrosion inhibitor using the modified water-soluble polymer obtained in the first step.

11. A lubricant, softener, surfactant, resin curing agent, or metal corrosion inhibitor containing the modified water-soluble polymer described in claim 6 or 7.

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