JPS59128353A - Novel alkenylsuccinic acid monoester salt, reactive surface active agent containing it, and high polymer improver containing it - Google Patents

Abstract

NEW MATERIAL:An alkenylsuccinic acid monoester salt shown by the formula I and/or formula II (R1 is hydrocarbon group which may contain substituent group; R2 is H, or methyl; A is 2-4C alkylene; M is monovalent or bivalent cation; n is positive integer of 1-50; m is ionic valence of M). EXAMPLE:Potassium 1-methacryloyloxyethyldodecenylsuccinic acid monoester. USE:Useful as a reactive surface active agent or an agent for improving high polymers. Polymers obtained by this reactive agent have especially improved permanent antistatic ability, anti-fogging properties, and compatibility with pigment. PROCESS:A compound shown by the formula III is reacted with a compound shown by the formula IV in the presence of a polymerization inhibitor such as preferably hydroquinone, etc. at 90-130 deg.C to give compounds shown by the formula V and formula VI. The compounds are then neutralized with a well- known base or its aqueous solution, to give compounds shown by the formula I and formula II.

Description

Detailed Description of the Invention The present invention provides compounds of the following formula (I) having a (meth)acrylic acid residue as a radically polymerizable group and/or (where R1 has a substituent) A good hydrocarbon group, Hiki indicates a hydrogen atom or a methyl group, A indicates the number of carbon atoms, m
The present invention relates to an alkenyl succinic acid monoester salt represented by l''Ji ionic value, a reactive surfactant composition containing the same, and a polymer modifying agent containing the same.

Conventionally, emulsion polymerization reactions have been carried out using non-reactive surfactants. However, in the emulsion produced by this method, the surfactant remains locally concentrated without being mixed with the polymer, so in the process of forming a film from the polymer, the surfactant is It was difficult to obtain a homogeneous polymer film.

It has been known that this non-uniformity of polymer films has an adverse effect on various properties such as dyeability, antistatic properties, weather resistance, and chemical resistance.

In order to eliminate these drawbacks, in recent years, molecules have been developed that contain both a group with surfactant ability and a group with polymerizability, which not only acts as an emulsifier for monomers, but also gradually incorporates them into the polymer during polymerization. More and more reactive surfactants are being developed and used.

As a result of intensive studies on reactive surfactants, the present inventors discovered that (meta) as a radical polymerizable group in the molecule.
The 2-alkenylsuccinic acid monoester salts represented by the above formula (1) or (II) having an acrylic acid residue are useful reactive surfactants; It was discovered that because there is an ether bond between a hydrogen group and a hydrophilic group such as a carboxylate group or a polyalkyleneoxy group, emulsion polymerization can be carried out under optimal conditions by changing the balance between hydrophilicity and lipophilicity depending on the monomer.

In addition, this alkenyl succinic acid monoester salt is
It is possible to impart hydrophilicity to a hydrophobic resin by using a reactive surfactant in a larger amount than that used in conventional emulsion polymerization, and it is also useful as a polymer modifying agent. I found out.

The present invention is based on the above findings, and an object of the present invention is to provide a novel alkenylsuccinic acid monoester salt represented by the above formula (1) or (11), a reactive surfactant containing the same, and a reactive surfactant containing the same. The purpose of the present invention is to provide a polymer modifying agent.

The compound represented by formula (I) or (II) of the present invention is produced, for example, according to the following formula.

(INJ side 2 and (1) and (...J (in the formula, R,, R,, A, M, n and n) have the above-mentioned meanings) The compound represented by the formula (I) which is the starting material is It can be obtained, for example, by addition reaction of α-olefin and maleic anhydride in an inert gas atmosphere according to a known method.

That is, when dodecene is used as the α-olefin, dodecenylcono-phosphate anhydride is obtained, and when octadecene is used, octadecenylcono-phosphate is obtained.

The compound represented by the general formula is an alkylene oxide adduct of acrylic acid or methacrylic acid, and must have an active hydroxyl group at the end. Examples of this compound include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate droxyethyl acrylate, and the like when 1 is 1.

Compounds where n is 1 or more include ethylene oxide adducts, propylene oxide adducts, butylene oxide adducts of (meth)acrylic acid, or block or random adducts thereof, and these compounds By arbitrarily selecting the value of n, it is possible to adjust the tI L B value of the compound (I) and/or ((1) of the present invention as a surfactant.

The synthesis of compounds (■ and (2)) from compounds (I) and GV) can also be carried out by a batch reaction, but as a preferred method, compound (l [) Heated to 130°C and added the compound (
A method of dripping IV) may be mentioned. During this reaction, in order to inhibit the polymerization of compound 11v), a known polymerization inhibitor,
For example, it is preferable to carry out the reaction in the presence of hydroquinone monomethyl ether, noihydroquinone, pyrogallol, catechol, benzoquinone, anthraquinone, phenothiazine, p-phenylenediamine, benzidine, nitrobenzene and the like. The compounds (■ and (B)) synthesized in this way are neutralized with a known base or an aqueous solution thereof, and are led to the compounds (I) and (U) of the present invention. The bases used in this case include: Examples include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and magnesium hydroxide, and organic bases such as ammonium hydroxide and monoalkylamines, dialkylamines, trialkylamines, and ethanolamines.Compounds From (■ and (b)), the present invention compound (1) and (
In leading to II), it is also possible to adjust the amount of these bases as necessary to adjust the degree of neutralization.

Ethylenically unsaturated monomers that can be subjected to emulsion polymerization using the compound (1) or (If) of the present invention thus obtained as a reactive surfactant include styrene derivatives, vinyl esters, acrylic esters, and methacrylates. Acid esters, α, β, β-carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, or salts thereof; acrylamide, methacrylamide, N-methylacrylamide,
α, β-unsaturated amides such as N-methylolacrylamide; acrylonitrimethacrylatelyl, vinyl chloride, hnyritene chloride, ethylene, α-olefins,
Conjugated dienes such as butadiene, alkyl vinyl ethers, alkyl vinyl ketones, maleic anhydride, maleic esters, itaconic esters, etc. are included. Also included are crosslinkable divinyl compounds such as divinylbenzene, ethylene glycol dimethacrylate, and methylene bisacrylamide.

When carrying out emulsion polymerization using the compound (1) or (U) of the present invention as a reactive surfactant, the reaction temperature is 0°C to 100°C, preferably 20°C to 90°C, and the polymerization is carried out in an inert gas. Polymerization can be carried out by adding an initiator and a polymerization regulator.

Methods for charging the polymerization initiator and polymerizable ethylenically unsaturated monomer into the reactor include charging the entire amount at the start of polymerization, or charging continuously as the polymerization reaction progresses. , Konera's method can be selected depending on the reactivity of the monomer and the composition of the desired copolymer. In the present invention, although it is possible to optionally use a common emulsifier in combination, a sufficiently stable emulsion can be obtained even with the reactive surfactant of the present invention alone, and even when used in combination, it can be used in a common emulsion polymerization method. A proportion smaller than the amount used is sufficient.

As the polymerization initiator used in the present invention, any known water-soluble radical polymerization initiator can be used. For example, inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate; known water-soluble organic peroxides; 1
This is a redox polymerization initiator system that uses iron in combination.

The amount of the compound (I) or (It) of the present invention used as a reactive surfactant can be varied depending on the type of polymer, the composition of the 7-mer, the purpose, the required performance, etc. When producing a hydrophobic polymer for the purpose of improving properties, antistatic properties, etc., the compound (I) or (II) of the present invention is usually added in an amount of 0.1 to 40% by weight (hereinafter simply referred to as titanium) in the copolymer. ), preferably 0.2-30%.

Moreover, the compound (1) or (II) of the present invention can also be used as a polymer modifier. That is, when used as the above-mentioned reactive surfactant, 10 to 80% of
A hydrophilic polymer (for example, a swellable resin) can be obtained from a monomer for producing a hydrophobic polymer by blending the monomers in an amount of 20 to 60, preferably 20 to 60.

By using the reactive surfactant of the present invention, it is possible to impart excellent dyeing properties, antistatic properties, water resistance, hydrophilicity, etc. to various polymers. That is, in the polymer produced using the reactive surfactant of the present invention, after polymerization, the hydrophilic groups resulting from the copolymerized surfactant are uniformly dispersed.
It is possible to improve the above-mentioned properties, particularly permanent antistatic properties, antifogging properties, and pigment miscibility.

Further, even if the reactive surfactant of the present invention is used in large amounts for the purpose of modifying a polymer, it will not remain in the polymer as it is because of its good copolymerizability. Therefore, polymer modifiers made of known monomers containing carboxyl groups or sulfo groups, such as sodium (meth)acrylate, sodium styrene sulfonate, sodium (meth)allylsulfonate, 2-acrylamide 2
- Unlike polymer modifiers containing sodium methylpropanesulfonate, water-soluble polymers do not form and deteriorate water resistance.

Furthermore, in the reactive surfactant of the present invention, the HLB value can be changed by adjusting the type of hydrocarbon group that is a hydrophobic group and the length of an alkyleneoxy group that is a hydrophilic group. It is also possible to improve the mechanical stability of the emulsion during polymerization and to contribute to the prevention of environmental pollution caused by residual surfactant in reaction wastewater.

Next, the present invention will be explained with reference to Examples.

Example 1 (1) Anhydrous dodecenyl? :-Ha < m 26.69- and hydroquinone monomethyl ether 14In11 were charged and heated to 100'C. 2
-Hydroxyethyl methacrylate-) 13.0. P was added dropwise over 2 hours, and stirring was continued for an additional hour.

As a result, a pale yellow liquid that was liquid at room temperature was obtained.

According to the results of measurement of the infrared absorption spectrum of the liquid, the absorptions at 1865 crn' and 178° Crn', which correspond to the carbonyl bonds of the acid and anhydride of dodecenylsuccinic anhydride, and the hydroxyl group of 2-hydroxyethyl methacrylate are caused. The absorption at 3500 Crn' disappears, and the newly generated ester bond 17 appears as a shoulder of the absorption at 1710 cm', which corresponds to the conjugated ester bond of methacrylic acid.
An absorption of 30 cm2,' appeared.

Further, from the results of nuclear magnetic resonance spectroscopy, the liquid is 1-methacryloyloxyethyldodecenylsuccinic acid and 4-methacryloyloxyethyldose represented by the following formulas (V') and □□□'). It was confirmed that it was decenylsuccinic acid.

IH-NMR (CDC4,) δ: Internal standard TMS0
．． 88 (31(t, J=7Hy) CH,-('-
fiv (kyl group terminal) 1.1-1.5 (14H, m) -CH2- (alkyl group) 1.7-2.2 (7H,, m) (methacrylic acid residue) (alkenyl group) 2.2 ~2.4
(2H, m) -CH,, -C-0- (succinic acid residue) 1 4.32 (4f(,s) -0-CH2CH2
-0" (-1-f vy group) 5.2 to 5.8
(3H,m) 1 (alkenyl group) (terminal olefin) 10.2 (IH,5)-CO,H (1t> I N- equivalent to the product obtained in (+)
A KOH aqueous solution was added to neutralize the mixture to obtain a 25% aqueous solution of 1-methacryloyloxyethyldodecenyl succinic acid monoester potassium salt and 4-methacryloyloxyethyldodecenyl succinic acid monoester potassium salt.

Examples 2 to 4 Hexadecenyl succinic anhydride 32.2P was used instead of dodecenyl succinic anhydride, and this was reacted with various (meth)acrylic acid derivatives under the same conditions as the reaction in Example 1 (1). , the compounds shown in Table 1 were obtained.

All of the reaction products obtained below were pale yellow viscous liquids at room temperature, and were confirmed to be the compounds shown in Table 1 above from the results of IR and NMR measurements.

These compounds were further neutralized with an equivalent amount of KOH to obtain 25% aqueous solution of each monoester potassium salt.

Example 5 An emulsion polymerization reaction was carried out using the reactive surfactants obtained in Examples 1 to 4.

The polymerization stability, polymerization conversion rate, and mechanical stability of the obtained polymer emulsion were measured, as well as the water resistance, hygroscopicity, and water absorption of the dry film obtained from the polymer emulsion. The results are shown in Table 2.

[Polymerization method]

A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel was charged with 5 oy of water, 0.55' of 7 y of persulfate, and 0.752 mol of sodium hydrogen carbonate.
The system is replaced with nitrogen gas and the temperature is raised to 70'GK. Into this reaction vessel, an emulsion obtained by adding a reactive surfactant of a predetermined size and type and a seven-spot of a predetermined size and type to 10 oz of water under stirring was added dropwise from a dropping funnel over a period of 2 hours. do. After the dropwise addition was completed, stirring was continued for 2 hours at 70°C to obtain a polymer emulsion.

[Monomer composition (weight ratio)] Composition a: Butyl acrylate/styrene (50150) Composition = styrene/methyl methacrylate/butyl acrylate (30/30/40) Composition C: Styrene/methyl methacrylate /butyl acrylate (30/35/35) [Measurement/evaluation method] Polymerization stability: Passed through a 100-mesh wire mesh, washed the filtered residue with water, dried at 105±2°C for 12 hours, and allowed to coagulate. Get lumps. This dry weight is expressed as weight percent relative to the monomer used.

Mechanical stability: Expressed by gravity relative to the latex solid content of the aggregate formed after stirring for 5 minutes using a Marlon tester under a load of 10 kg.

Hygroscopicity: A film with a thickness of approximately 0.3 rttx was made from the emulsion, dried at 40°C-30%RH for 24 hours, and then dried at 20°C-30%RH for 24 hours.
It is expressed as the amount of moisture absorbed per unit surface area after being left for 24 hours at 95% RH.

Water absorption: It is expressed as the amount of water absorbed per unit weight of a film formed from an emulsion with a thickness of approximately 0.3 myi after being immersed in water for 24 hours.

Water resistance: Approximately (13 m, based on the time required for whitening of a W membrane by water immersion method, ◎: 1 day or more, 081 hours or more, less than x 11 hours, XX = instantaneous).

(Note 1) * Regarding these items, I11 was not determined.

(Note 2) ** Because it becomes cloudy in water and disperses, it cannot be expressed as a negative number.

(Note 3) + Perex SS Dotecyl diphenyl ether disulfo disodium phosphate that's all 285-1

Claims (1)

[Scope of Claims] 1. The following formula (I) and/or (U) (wherein) represents a hydrocarbon group which may have a substituent,
)4 represents a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, and M represents a monovalent or divalent cation. n represents a positive number from 1 to 50, and m represents the ionic valence of M). 2. The following formula (I) and/or (If) also (wherein, Ro represents a hydrocarbon group which may have a substituent, R
2 represents a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, and M represents a monovalent or divalent cation. A reactive surfactant containing an alkenylsuccinic acid monoester salt represented by n (n is a positive number from 1 to 50 and m is an ionic valence of M). 3. The following formula (1) and/or (It), 2 (in the formula, 1 represents a hydrocarbon group that may have a substituent
2 represents a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, and M represents a monovalent or divalent cation. A polymer modifier containing an alkenylsuccinic acid monoester salt represented by n (n is a positive number from 1 to 50, and m is an ionic valence of M).