JP2017128669A - 2-methyleneglutaric acid ester-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a 2-methyleneglutaric acid-based polymer excellent in salt resistance and rust-preventing properties.SOLUTION: The 2-methyleneglutaric acid ester-based polymer has a structural unit represented by formula (1). (Rand Reach independently represent hydrogen, an ammonium salt, an organic amine salt, a metal salt, or a 1-10C alkyl group substituted with one or more hydrophilic groups, provided that at least one of Rand Rrepresents a 1-10C alkyl group substituted with one or more hydrophilic groups.)SELECTED DRAWING: None

Description

The present invention relates to a 2-methylene glutarate ester-based polymer having a hydrophilic substituent.

A polymer having a 2-methyleneglutaric acid structure is known to be useful for a fiber treatment agent, a water treatment agent, a pigment dispersant and the like because of its characteristic structure. For example, a homopolymer of 2-methyleneglutaric acid is known to have excellent clay dispersibility as a detergent additive (Patent Document 1). It is also known that a copolymer of 2-methyleneglutaric acid and acrylic acid is useful as a fiber treatment agent (Patent Document 2).

JP 2012-72278 A International Publication No. 2011/118200

While the 2-methylene glutaric acid-based polymer has various excellent properties, when it is used as an aqueous solution, it has a drawback that it is precipitated by addition of a salt and the viscosity is lowered. The object of the present invention is to improve salt resistance while maintaining the hydrophilicity of a 2-methyleneglutaric acid polymer.

The present inventors have intensively studied to solve the above problems, and that the above problems can be solved by using a 2-methylene glutarate ester-based polymer having a structural unit represented by the following general formula (1). I found.

(R ₁ and R ₂ each independently represents hydrogen, an ammonium salt, an organic amine salt, a metal salt, or an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups, and at least one of them is Represents an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups.)

Since the 2-methylene glutarate ester-based polymer of the present invention is a hydrophilic polymer having a methylene glutarate polymer skeleton, it becomes a polymer having improved salt resistance while retaining the characteristics of the methylene glutarate polymer, and a fiber treatment agent. And pigment dispersants.

2 is a ¹ H-NMR chart of a homopolymer of diglyceryl 2-methyleneglutarate obtained in Example 1. FIG. 2 is a ¹ H-NMR chart of a 2-methyleneglutaric acid homopolymer obtained in Comparative Example 1. 2 is a ¹ H-NMR chart of a diglyceryl 2-methyleneglutarate / butyl acrylate copolymer obtained in Example 3. FIG.

The present invention will be described below. A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
The 2-methylene glutarate ester polymer of the present invention is a 2-methylene glutarate ester polymer having a structural unit represented by the following general formula (1).

(R ₁ and R ₂ each independently represent hydrogen, an ammonium salt, an organic amine salt, a metal salt, or an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups, and at least one of them. Represents an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups.
A 2-methyleneglutaric acid ester-based polymer, wherein R ₁ and / or R ₂ is an alkyl group having 1 to 10 carbon atoms substituted with a nonionic hydrophilic group, is a preferred embodiment of the present invention. One.
Moreover, the 2-methylene glutarate ester polymer in which R ₁ and / or R ₂ has the structure of the formula (2) is one of the preferred embodiments of the present invention.

In the above formula (1), R ₁ and R ₂ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups, and at least one of them represents one or more hydrophilic groups. And an alkyl group having 1 to 10 carbon atoms substituted with a functional group. R ₁ and R ₂ may be linear or branched, and may be cyclic or may have a structure partially including a ring. The alkyl group substituted with one or more hydrophilic groups means a group having a structure in which one or more hydrogen atoms contained in the alkyl group are replaced with hydrophilic groups.
The hydrophilic group may be anionic, cationic, amphoteric, or nonionic, and examples of the anionic hydrophilic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the cationic group include an amino group, an imino group, a quaternary ammonium group, and examples of the amphoteric group include a carbobetaine group, a sulfobetaine group, and a phosphobetaine group. Nonionic groups include hydroxyl groups; amide groups; cyclic lactam groups such as pyrrolidone groups and caprolactam groups; alkoxy groups; polyoxyalkylene groups such as polyoxyethylene groups and polyoxypropylene groups;

  Of these, nonionic groups are preferred, and hydroxyl groups are more preferred. Specific examples of the alkyl group substituted with a hydroxyl group include hydroxyethyl group, hydroxypropyl group, hydroxypentyl group, hydroxyhexyl group, 1,2-dihydroxypropyl group, 1,3-dihydroxypropyl group, 2,3- Dihydroxypropyl group, hydroxyethyloxyethyl group, 1,2-dihydroxypropyloxyethyl group, 1,3-dihydroxypropyloxyethyl group, 2,3-dihydroxypropyloxyethyl group, trishydroxymethylmethyl group, trishydroxymethylethyl Group, trishydroxymethylpropyl group, glycosyl group and the like.

  In addition, it is also one of the preferred embodiments that the nonionic group is a pyrrolidone group. Specific examples of the alkyl group substituted with a pyrrolidone group include a pyrrolidone methyl group, a pyrrolidone ethyl group, a pyrrolidone ethoxyethyl group, Examples include pyrrolidone ethoxypropyl group.

  Examples of the alkyl group substituted with the alkoxy group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a butoxymethyl group, a butoxyethyl group, and a butoxypropyl group. It is done.

  The organic amine salt is a primary to quaternary amine salt, and preferably an amine salt having 1 to 20 carbon atoms. Examples of the metal salt include alkali metal salts such as lithium salt, sodium salt and potassium salt; alkaline earth metal salts such as calcium salt; transition metal salts such as iron salt and zinc salt;

<Composition>
The content of the structural unit represented by the above formula 1 in the 2-methyleneglutarate polymer of the present invention is preferably 5% by mass or more. More preferably, it is 20 mass% or more. More preferably, it is 40 mass% or more. When the content of the structural unit of Formula 1 is within the above range, functions such as salt resistance and hydrophilicity derived from the 2-methylene glutarate ester structure tend to be exhibited well. A homopolymer consisting only of the structural unit of the above formula 1 is also a preferred embodiment of the present invention. That is, the upper limit of the content of the structural unit of the formula 1 in the 2-methylene glutarate ester polymer of the present invention is preferably 100% by mass.

  The 2-methylene glutarate ester polymer of the present invention may contain a structural unit other than the structural unit represented by the above formula 1. For example, a structural unit derived from a copolymerizable monomer described later may be included. The structural unit derived from a copolymerizable monomer is a structural unit produced by polymerization of a copolymerizable monomer, and specifically, at least one carbon-carbon double bond contained in the copolymerizable monomer. Is a structural unit having a structure in which a carbon-carbon single bond is replaced.

<Molecular weight>
The molecular weight of the 2-methylene glutarate ester-based polymer of the present invention is not particularly limited, but the weight average molecular weight (Mw) is preferably a lower limit of 1,000 or more and an upper limit of 10,000,000 or less. More preferably, the lower limit is 5,000 or more and the upper limit is 5,000,000 or less.
If it is the said range, there exists a tendency for intensity | strength, a dispersibility, the solubility to a solvent, and the handleability of a solution to improve.
The molecular weight can be obtained by measurement by gel permeation chromatography described later.

<Manufacturing method>
The 2-methylene glutarate ester polymer according to the present invention can be obtained, for example, by polymerizing a monomer component containing a monomer represented by the following formula (3).

(R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups, and at least one of them is substituted with one or more hydrophilic groups. Represents an alkyl group having 1 to 10 carbon atoms.)
The monomer of the above formula (3) may be used alone or in combination of two or more.
The monomer component is not particularly limited as long as it contains at least the monomer of formula (3). For example, the monomer of formula (3) may be used alone, Any monomer copolymerizable with the monomer (3) may be used in combination. In addition, when the monomer other than the monomer of the formula (3) is copolymerized, the content of the monomer of the formula (3) in the monomer component is not particularly limited. The content of the monomer of formula (3) in the monomer component is preferably 5% by mass or more, more preferably 20% by mass or more, and further preferably 40% by mass or more. preferable.

<Copolymerizable monomer>
The monomer copolymerizable with the monomer of the formula (3) is not particularly limited, and specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) (Meth) acrylic acid esters such as butyl acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate; (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide (Meth) acrylamide derivatives such as N, N-dimethyl (meth) acrylamide; basic unsaturated monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinylimidazole, etc. And salts or quaternized compounds thereof; N-vinylformamide, N-vinyloxazolide N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide; (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. Carboxyl group-containing unsaturated monomers and salts thereof; unsaturated anhydrides such as maleic anhydride and itaconic anhydride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethylene carbonate and derivatives thereof; styrene And its derivatives; ethyl (meth) acrylic acid-2-sulfonate and derivatives thereof; vinyl sulfonic acid and derivatives thereof; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; ethylene, propylene, octene, butadiene and the like; Olefins; Etc., and the like.
These may use only 1 type and may mix 2 or more types and may be copolymerized with the monomer of Formula (3). Moreover, random copolymerization may be sufficient and block copolymerization and graft copolymerization may be sufficient.

<Polymerization method>
The method of the polymerization reaction (sometimes referred to as “polymerization step”) for obtaining the 2-methylene glutarate ester polymer according to the present invention is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, and emulsion polymerization. , Suspension polymerization, precipitation polymerization, and other conventionally known methods.
In addition, as a polymerization method for obtaining the 2-methylene glutarate ester polymer according to the present invention, a static polymerization method is preferably employed from the viewpoint of physical properties of the obtained polymer. The stationary polymerization method refers to polymerization that does not involve forced stirring using a stirrer during polymerization, and the raw materials may be uniformly mixed in advance with a stirrer before polymerization. The static polymerization method may be a batch method or a continuous method, and the continuous method is preferably polymerization using a movable belt. In the case of a batch system, for example, there is a method of starting polymerization by adding a monomer composition, a solvent, a polymerization initiator to a reactor, mixing using a stirrer, stopping stirring and raising the temperature. .

<Polymerization solvent>
The solvent used in the polymerization reaction is not particularly limited. For example, water; aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran, dioxane and the like And ether solvents. These solvents may be used alone or in combination of two or more. In addition, water is preferable as a preferable polymerization solvent, but a solvent that dissolves in water, for example, an alcohol selected from methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, diethylene glycol, and the like alone or in combination of two or more kinds of It can also be used as a mixture. In particular, when a solvent such as isopropyl alcohol or n-butyl alcohol is mixed with water, the boiling point of water, that is, the polymerization temperature is lowered by azeotropic action, which is preferable from the viewpoint of suppressing side reactions.
<Polymerization temperature>
When performing the polymerization reaction, the reaction conditions such as the reaction temperature are not particularly limited. For example, the reaction temperature is preferably 20 to 150 ° C.

<Polymerization initiator>
The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, and t-butylperoxyisopropyl. Organic peroxides such as carbonate and t-amylperoxy-2-ethylhexanoate; hydrogen peroxide; persulfates such as potassium persulfate and ammonium persulfate; 2,2′-azobis (isobutyronitrile); And azo compounds such as 1,1′-azobis (cyclohexanecarbonitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile); These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used may be set as appropriate according to the combination of the polymerizable monomers and the reaction conditions, and is not particularly limited.
The amount of the initiator used is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.5 to 3% by mass with respect to the polymerizable monomer component. % Is even more preferred.

  When the polymerization reaction is performed, a conventionally known transition metal salt can be used for the purpose of promoting the polymerization reaction. Specific examples of the transition metal salt include carboxylates and chlorides such as copper, iron, cobalt, and nickel. These may be used alone or in combination of two or more. May be. When the transition metal salt is used, the amount used is not particularly limited, but is preferably 0.1 to 20000 ppb, more preferably 1 to 5000 ppb in terms of mass ratio with respect to the polymerizable monomer component. When performing the polymerization reaction, in addition to the polymerization initiator and, if necessary, the pH adjuster and the transition metal salt, any chain transfer agent, buffering agent, etc. can be used as necessary. .

  The 2-methylene glutarate ester-based polymer of the present invention may be produced including steps other than the polymerization step. Examples of the process that can be included include a drying process, a concentration / dilution process, a catalyst deactivation process, a purification process, a transesterification process, and a hydrolysis process.

<Use of 2-methylene glutarate ester polymer of invention>
As described above, since the 2-methylene glutarate ester polymer according to the present invention has hydrophilicity and excellent salt resistance, it is assumed that it is used in environments having various salt concentrations. , Shampoos, rinses, dish detergents, clothing detergents, cosmetics and the like. Moreover, it can use suitably as an organic pigment, an inorganic pigment, various fillers, a filler, and a chemical | medical agent dispersing agent. Moreover, since salt resistance is excellent, since it is excellent in mixing stability with various materials, it can be used suitably as various hydrophilicity imparting agents. For example, it is also suitable as a fiber treatment agent that is added to polyester fiber, nylon fiber, acrylic fiber, or the like, or is coated with a surface to improve hygroscopicity. Further, it can be used in various applications such as paints such as antifouling paints and ship bottom paints, resin modifiers, inks, ink receiving layers, various surface treatment agents, various primers, and various binders.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by these Examples. Unless otherwise specified, “parts” hereinafter represents “parts by mass”.

<Gas chromatography>
GC-2010 (manufactured by Shimadzu Corporation) was used, and measurement was performed with a capillary column DB-17HT L30 m × ID 0.25 mm and DF 0.15 mm.
When measuring the peak area, the left and right base lines of the peak were connected by a straight line, and the area surrounded by the base line and the peak was measured as the peak area.

<Weight average molecular weight>
The weight average molecular weight is a gel permeation chromatograph (GPC system, manufactured by Tosoh Corporation), using a column in which TSKgel SuperH3000, TSKgel SuperH4000, and TSKgel SuperH5000 are connected to each other, and tetrahydrofuran is used as the eluent, in terms of polystyrene. Determined by

<Synthesis Example 1>
(1) Synthesis of 2-methyleneglutarate diisopyrideneglyceryl (MG-2iPGL) A reaction vessel containing a stirring bar was equipped with a Dean-Stark device equipped with a gas introduction tube, thermometer, reflux tower and cooler. Dimethyl 2-methyleneglutarate (MG-2M) 30 g, 2,2-dimethyl-1,3-dioxolane-4-methanol (DOM) 120 g, dibutyltin oxide 1.8 g, and mixed with oxygen / nitrogen through a gas introduction tube The reaction solution was stirred while blowing gas (oxygen concentration 7%), and heated in an oil bath (bath temperature 130 ° C.) to initiate transesterification under a reduced pressure of 10 kPa. While the generated methanol was distilled off, the decrease in MG-2M was followed by gas chromatography (GC) analysis, and the reaction was completed in 12 hours. The mixture was cooled to room temperature, 75 g of saturated brine and 150 g of ethyl acetate as an extraction solvent were added, the mixture was transferred to a separatory funnel, and the organic layer and the aqueous layer were separated. The organic layer was washed several times with 75 g of water to remove excess raw material alcohol, and then the light boiling component was distilled off under reduced pressure to obtain 42 g of diisopyrideneglyceryl 2-methyleneglutarate (MG-2iPGL). .

(2) After adding 300 ml of methanol and 30 g of MG-2iPGL to a flask provided with a deprotection gas introduction tube for MG-2iPGL, 50 g of solid acid catalyst amberlist that had been pre-immersed in water and then air-dried was charged and gas was introduced. The reaction solution was stirred with a paddle blade while an oxygen / nitrogen mixed gas (oxygen concentration: 7%) was blown through the tube to start the deprotection reaction at room temperature. The disappearance of the MG-2iPGL spot and the production of intermediate and target product spots were confirmed by thin layer chromatography, and the reaction was completed in 24 hours. The filtrate obtained by filtering off the solid acid catalyst was washed with n-hexane, unreacted MG-2iPGL was removed, and the product obtained by concentration under reduced pressure was isolated on a silica gel column (mobile phase methanol / ethyl acetate), 10 g of light yellow transparent liquid of the target diglyceryl 2-methylene glutarate (MG-2GL) was obtained.

<Example 1>
A reaction vessel containing a stirrer was equipped with a gas introduction tube, a thermometer, and a cooling tube, and 5.0 g of MG-2GL synthesized in Synthesis Example 1 as a monomer, 5.0 g of ion-exchanged water as a solvent, an azo radical 0.025 g of a polymerization initiator (trade name: V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and stirring and heating were started while flowing nitrogen gas. Stirring was stopped at an internal temperature of 50 ° C., and the polymerization reaction was carried out by allowing the mixture to stand for 12 hours. The obtained reaction liquid was diluted with acetone, and poured into a large amount of n-hexane while stirring to reprecipitate to obtain a solid polymer (MG-2GL homopolymer, hereinafter referred to as PM2G polymer). The obtained polymer had a weight average molecular weight of 335,000. A ¹ H-NMR spectrum (heavy solvent: heavy water) of the obtained PM2G polymer is shown in FIG.

<Comparative Example 1>
A polymerization reaction or the like was carried out in the same manner as in Example 1 except that MG-2GL was changed to 2-methyleneglutaric acid to obtain a 2-methyleneglutaric acid homopolymer (hereinafter referred to as PMGA polymer). Since no peak appeared in GPC under the conditions of the example, the molecular weight could not be specified. FIG. 2 shows the ¹ H-NMR spectrum (heavy solvent: heavy water) of the obtained PMGA polymer.

<Example 2 (Salt tolerance evaluation)>
An aqueous solution of PMG2G polymer was adjusted to pH 7-8 with an aqueous NaOH solution, and further diluted with ion exchange water to prepare an aqueous solution having pH 7-8 and a concentration of 1%. Similarly, an aqueous solution of PMGA polymer having a pH of 7 to 8 and a concentration of 1% was prepared.
A calcium chloride aqueous solution was gradually added to each, and the state change was observed. The viscosity of the PMGA polymer markedly decreased with the addition of the aqueous calcium chloride solution, and the aqueous solution became cloudy and became emulsified until the calcium concentration reached 0.1 mol / L.
On the other hand, with the PMG2G polymer, the viscosity was slightly lowered with respect to the addition of the calcium chloride aqueous solution, there was no change in appearance, and even when the calcium concentration reached 0.5 mol / L, it did not become cloudy.
From the above observations, it was clear that the PMG2G polymer was superior in salt resistance compared to the PMGA polymer.

<Example 3>
A reaction vessel containing a stirrer was provided with a gas introduction tube, a thermometer, and a cooling tube, and 2.0 g of MG-2GL synthesized in Synthesis Example 1 as a monomer, 3.0 g of butyl acrylate (BA), and methanol 5 as a solvent 0.0 g and an azo radical polymerization initiator 0.025 g (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) were charged, and stirring and heating were started while flowing nitrogen gas. Stirring was stopped at an internal temperature of 50 ° C., and the polymerization reaction was carried out by allowing the mixture to stand for 12 hours. The obtained reaction solution was diluted with acetone and poured into a large amount of n-hexane while stirring to reprecipitate to obtain a solid polymer (P (M2gB) polymer). The obtained polymer had a weight average molecular weight of 346,000. The ¹ H-NMR spectrum (deuterated solvent: deuterated chloroform) of the obtained P (M2gB) polymer is shown in FIG.

<Reference example (contact angle measurement)>
A 0.5% MEK solution of the P (M2gB) polymer obtained in Example 3 was prepared, and a thin film of P (M2gB) polymer was formed on the PET film with a spin coater. When the contact angle of the P (M2gB) polymer surface was measured by the underwater bubble method, it was 164 °. When the contact angle of the PET film as the base material was measured in the same manner, it was 117 °. From this, it was shown that P (M2gB) polymer is useful as a surface hydrophilizing agent.

Claims (3)

A 2-methylene glutarate ester polymer having a structural unit represented by the following formula (1).

(R ₁ and R ₂ each independently represents hydrogen, an ammonium salt, an organic amine salt, a metal salt, or an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups, and at least one of them is Represents an alkyl group having 1 to 10 carbon atoms substituted with one or more hydrophilic groups.) The 2-methylene glutarate ester-based polymer according to claim _1, wherein R ₁ and / or R ₂ in formula (1) is an alkyl group having 1 to 10 carbon atoms substituted with a nonionic hydrophilic group. A 2-methyleneglutaric acid ester polymer in which R ₁ and / or R ₂ in the formula (1) is a structure of the following formula (2).

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