JPS59116249A - Novel alkenylsuccinic acid monoester salt, reactive surface active agent and improver for high polymer 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; R2 is H, or CH3; A is 2-4C alkylene; M is monovalent or divalent cation; n is 0-100; m is ionic valence of M). EXAMPLE:Potassium 1-allyldodecenylsuccinate and potassium 4-allyldodecynylsuccinate. USE:A reactive surface active agent and an improver for high polymer. Providing various kinds of polymers with improved dyeability, antistatic properties, water resistance, hydrophilic properties, etc., especially contributing to improvement of permanent antistatic properties, anti- fogging properties, improvement of chemical stability of emulsion during polymerization, and prevention of environmental pollution caused by surface active agent remaining in waste water of reaction. PROCESS:A compound shown by the formula III is reacted with a compound shown by the formula IV preferably in the presence of a polymerization inhibitor under heating at 90-160 deg.C to give a compound shown by the formula V and a compound shown by the formula VI, which are neutralized with a base shown by the formula VII or its aqueous solution to give a compound shown by the formula I and a compound shown by the formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compounds of the following formula (1) containing a (meth)allyl group as a radically polymerizable group and/or 2 (where l<1 has a substitution of 2 R2 represents a hydrogen atom or a methyl group, and A represents a carbon group with a carbon number of 2.
to 4 alkylene groups, and M represents monovalent or divalent ion resistance. (n represents the number of stops from O to 100, and m represents one ion of M). And it flashes on the Sono Molecular Reform Agent.

Conventionally, the emulsification reaction has been carried out using a non-reactive agent. However, in the emulsion produced by this, the surfactant is locally produced and remains without being mixed with the polymer, so in the process of forming a film from the polymer, the surfactant is It was difficult to maintain a homogeneous polymer film. It has been known that this non-uniformity of polymer films adversely affects various properties such as vermilion, antistatic properties, weather resistance, and chemical resistance.

In recent years, in order to eliminate the drawbacks of monomers, a group with surfactant ability and a group with monomerization have been added to the molecule, which not only acts as an emulsifying agent for monomers, but also
Gradually incorporated into polymers, surfactants have been developed and are now in use.

Akina Fuji et al. congratulate the reactive surfactants.
After much research, we discovered that (
Asolekenyl succinic number monoester salts represented by formula (1) or atomyl having a meta)allyl group are useful anti-KE surfactants; Because there is an ether bond between the hydrogen group and the hydrophilic carboxylate group and polyalkyleneoxy group, it is possible to balance hydrophilicity and oil resistance depending on the monomer and carry out emulsification under optimal conditions. I discovered that.

In addition, if the alkenyl succinic monoester salt is used in a larger amount than the amount of reactive surfactant used in normal emulsion polymerization, hydrophilicity can be imparted to a hydrophobic resin, and polymer modification It was also found to be useful as a quality agent.

The present invention is based on the above findings, and therefore, the object of the present invention is to provide a novel alkenyl amber monoester salt represented by the formula (1) or (n) and a reactive surfactant containing the same. The present invention provides a polymer modifying agent and a polymer modifying agent.

The compound represented by formula (1) or (11) of the present invention is manufactured according to the following formula.

(In the formula, R1% R2, A -, M% n and m are the same as the above-mentioned precursor.) The compound represented by the formula (2), which is a starting material, can be converted to α- by a known method, for example. It is obtained by addition reaction of olefin and maleic anhydride in an inert gas atmosphere.

That is, when dodecene is used as the α-olefin, dodecenylsuccinic anhydride is obtained, and when oftatecene is used, octadecenylsuccinic acid is obtained.

Further, the compounds represented by the general formula are allyl alcohol or methallyl alcohol and alkylene oxide adducts thereof.

The alkylene oxide adduct can be obtained, for example, by reacting allyl alcohol or methallyl alcohol with alkylene oxide in a stirred pressurized reactor in the presence of a potassium hydroxide catalyst.

From compound (l!l) and 0■ compound (V) and (vl)
For example, to synthesize 0() in a reaction vessel from 90 to
It is possible to use a method in which the mixture is heated to 160° C. and dripped onto the surface, or a method in which both are added at once. At this time, a solvent may or may not be used. In order to further prevent the polymerization of compound (Y), known polymerization inhibitors such as hydroquinone monomethyl ether, hydroquinone, pyrogallol, catechol, benzoquinone, anthraquinone,
Preferably, the reaction is carried out in the presence of phenothiazine, p-phenylenediamine, benzidine, nitrobenzene, or the like.

Compounds ① and (Vl) synthesized in this manner are neutralized with a known base or a water bath thereof, and are led to the compound (1) of the present invention and the compound. Bases used in this case include inorganic bases such as potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, and lithium hydroxide; and organic bases such as monoalkylamines, dialkylamines, trialkylamines, and ethanolamines. Examples include bases. In deriving the compounds (1) and (ID) of the present invention from the compounds (■ and (VD), it is also possible to adjust the degree of these bases as necessary to adjust the degree of the base.

Ethylenically unsaturated monomers that can be emulsified using the thus obtained compound (1) or (II) of the present invention as a reactive surfactant include styrene derivatives, vinyl esters, acrylic esters, methacrylic acid esters, acrylic acid, methacrylic acid, crotonic acid and other α, β, and β-carboxylic acids or their salts niacrylamide, methacrylamide, N-methylacrylamide,
α,β unsaturated amides such as N-methylol acrylamide, acrylonitrile, tacrylonitrile, vinyl chloride, vinylitine chloride, ethylene, α-olefin,
These include conjugated dienes such as butadiene, alkyl vinyl ethers, alkyl vinyl ketones, maleic anhydride, maleic esters, itacon esters, and the like.

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 (it) of the present invention as a reactive surfactant, the reaction temperature is 0°C to 100°C, preferably 20°C to 90°C, and polymerization is initiated in an inert gas. The agent and the polymerization modifier can be added and combined.

The polymerization initiator and the polymerizable ethylenically unsaturated monomer can be charged into the reactor by charging the entire amount at the start of the first reaction, or continuously as the first reaction progresses. However, these methods can be selected depending on the reactivity of the monomer and the composition of the desired copolymer. Although it is possible to optionally use a conventional emulsifier in combination with the present invention, a sufficiently stable emulsion can be obtained using only the reactive surfactant of the present invention, and when used in combination, a conventional emulsifying chamber method can be used. A smaller proportion than the child used in is sufficient.

As the polymerization initiator used in the present invention, any known water-soluble radical 1 polymerization initiator can be used. For example, inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, known water-based organic peroxides, or reducing sulfoxy compounds such as sodium bisulfite and sodium thiosulfate, and sulfuric acid 1
This is a redox 1 initiator system that uses iron in combination.

The amount of the compound (1) or (...) of the present invention used as a reactive surfactant can be varied depending on the type of polymer, monomer composition, purpose, required performance, etc.; When producing a hydrophobic polymer for the purpose of antistatic properties, the compound (1) of the present invention or the mark is usually present in the copolymer in an amount of 0.1 to 40% by weight (hereinafter simply %).
), preferably 0.2 to 30%.

Moreover, the compound (1) or (ll) of the present invention can also be used as a polymer rebonding agent. That is, when used as the above-mentioned reactive surfactant, if it is blended in a proportion of 10 to 80%, preferably 20 to 60%, in the monopolymer, the water uptake ability is improved from the monopolymer that produces the hydrophobic monopolymer. A polymer (the base is a swellable resin) can be obtained.

By using the reactive surfactant of the present invention, it is possible to impart maroon color properties, antistatic properties, water resistance, water uptake properties, etc. that are inferior to valley m1 coalescence.

That is, in the polymer produced using the reactive surfactant of the present invention, the water-absorbing groups resulting from the co-merged surfactant are uniformly dispersed after the nail bed, so that the above properties are improved, especially The same properties as those described above can be achieved in terms of anti-hyukuteiden properties, anti-fogging properties, and compatibility with black materials.

In addition, even if the reactive surfactant of the present invention is used in large quantities for the purpose of modifying a polymer, it remains in the polymer due to its good copolymerizability. Never. Therefore, known polymer modifiers made of monomers containing carboxyl groups or sulfo groups, such as sodium (meth)acrylate, sodium styrene sulfone, sodium (meth)allylsulfone, 2-acrylamide, 2-menalfuro, etc. S containing pansulfone sensitive sodium
Unlike molecular modifiers, water bath 8: 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 the hydrophobic group, which is the reconstituted water ligation group, and the length of the alkyleneoxy group, which is the water-absorbing group. As a result, it is possible to improve the chemical stability of the emulsion during polymerization and to contribute to the prevention of environmental pollution caused by residual interfacial viscosity agents in reaction waste water.

Next, examples will be presented to explain the unexploded EJA, but the present invention is not limited to these examples.

Rush current? ! I 1 (1) In a 1 t glass reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, add anhydrous tothycenyl.
l<1W324r Allyl alcohol 587 and hydroquinone monomethyl ether 140η were charged at 140℃~1
The mixture was stirred at 50° C. for 5 hours, and a colorless liquid was obtained which was liquid at room temperature.

The evaporation value of the Yoshi liquid was 172.0, and the saponification value was 345.2.

According to the measurement results of the infrared absorption spectrum of the liquid, absorptions at 1 865 cm and 1780 cm originate from the carbonyl bond of tothycenylsuccinic anhydride, and absorption at 3 300 cm originates from the hydroxyl group of allyl alcohol. c.
The absorption of m-” disappears and the ester bond becomes compatible 1 7
30 cn-' absorption and 17 due to carboxylic acid.
A new absorption at 00 cm-' appeared.

Furthermore, as a result of nuclear resonance spectroscopy, Katana et al. confirmed that the liquids were 1-allyldodecenylsuccinic acid and 4-allyldodecenylsuccinic acid represented by the following formulas (V') and (Vl'). O II (-NMR (CC1,) δ: Internal standard TMS0.8
8 (3I (, t, J = 7Hz) CHs- (alkyl group terminal) 1.1-1.5 (14H, m) -CH2-
(Alkyl group) 2.2-2.4 (2) I p m )
-CH2-C-0- (succinic acid residue) 1 4.6 (2H2m) -0-CH2-C= (
Allyl group) 5.0-5.5 (2H, m) =CH
2(')5.4 (2K', m) -CH=
CI (-(alkenyl group) 5.6-6.3 (I Hz
m) -CH=(allyl group) 11.5 (IH,
s) -C02f ((ii) The raw nails obtained in (t) were neutralized by adding an equivalent amount of IN-KOH water bath solution, and 25% of 1-allyldodecenyl, potassium uccinate and 4-allyldodecenyl potassium succinate were added. % aqueous solution was obtained.

Laughter Example 2 (1) Dialene 168 (
Manufactured by Mitsubishi Kasei Corporation: Alkenyl succinic anhydride (saponification value 351, iodine value 61) synthesized from a mixture of α-olefins with return elements of 16 and 18, iodination (105) and maleic anhydride (saponification value 351, iodine value 61) 241? and allyl alcohol adduct 1301 with an average of 2 moles of ethylene oxide were charged, and the mixture was stirred at 140 to 150°C for 5 hours under a gas stream to obtain a pale yellow liquid that was liquid at room temperature.

According to the results of measurement of the infrared absorption spectrum of the liquid, the absorption of 3450 crn-1 due to the hydroxyl group of the allyl alcohol ethylene oxide adduct disappeared, and a characteristic absorption similar to that in Example 1 appeared. .

Further, from the results of nuclear magnetic resonance spectroscopy, it was confirmed that the liquid was a compound represented by the following (Vri and (vr5).

R-C rise=cu-cH2-cn-coo(CH2CH2
O) 2-CM2-CH=CI(2CH2COOH (■") and R-CH=CH-CM2-CM-COOHCM2-C0
0(CH2CH20)2-C1(2CH=CH2(Vl
”) (In the formula, R is Cl5H27- and C15H31-.) (ii) Add an equivalent amount of l to the raw nail material obtained in (i).
It was neutralized by adding N-NaOH water m* to obtain a 25% aqueous solution of the above (V') and/or (Vi'').

Example Example 7 #4 Alkenylsuccinic anhydride used in Example 2 241
Use t to implement this! Reaction table for l 1 (i)
1 Note *) EO: Ethylene oxide ※*) PO: Propylene oxide Example 6 A pale yellow liquid at room temperature was produced in the same manner as in Example 2 except that methacrylic alcohol 72F was used instead of 130F, an average 2-mole adduct of ethylene oxide of allyl alcohol. ~Yellow liquid was obtained.

The acid value of this product is 143.1. Saponification value is 286.2,
The iodine value was 114.6. Instrumental analysis confirmed that the structure of this product is expressed by the following formula.

CH3 R-CH=CH-CH2CHCOOCH2-C=CH2
CM, COOH and R-CH=CH-CH2-CM-COOHcnzcOO
cH=c=CH2 SaH3 (wherein R is C13H27- and C15H31-)
Example J Instead of methacrylic alcohol 72M', lower equimolar ff
Using the alkylene oxide adduct of methacrylic alcohol shown in Example 6, the reaction was carried out in the same manner as in Example 6, to obtain the following compound.

Below is blank space 9.Example 8 Emulsion polymerization reaction was carried out using the reactive surfactants obtained in Examples 1 to 5.

Regarding the obtained polymer emulsion, its polymerization stability, polymerization conversion rate, mechanical stability, and water resistance of a dry film obtained from the polymer emulsion were measured. The results are shown in Table 3.

[1 cup method] In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, add 50 fl of water and 0 ammonium persulfate.
．． Charge 0.75 f of 5ts sodium hydrogen carbonate, replace the inside of the system with nitrogen gas, and raise the temperature to 70°C. In this reaction vessel, a reactive surfactant of a given type and type is added under stirring;
Similarly, an emulsion obtained by adding monomers of a specified type and type to 1001 water is added dropwise from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, stirring was continued for another 2 hours at 70°C to obtain a single combined emulsion.

[Monomer strap for convenience (weight ratio)]

Butyl acrylate/styrene (50150) [Measurement/evaluation method] 1-coat stability: Filtered through a 100-mesh wire mesh, washed the filtration residue with water, and dry-recorded at 105 ± 2°C for 12 hours to determine the coagulum. get. This dry quantity is expressed as % by weight relative to the toilet monomer.

Mechanical stability: Expressed as % by weight of the agglomerate formed after stirring for 5 minutes, based on the latex solid content, in a Marlon tester under an xoQ load.

Water resistance: Evaluated based on the time required for whitening by immersing approximately 0.3 mm in water on the basis of 021 days or more, ○: 1 hour or more, ×: less than 1 hour, XX: instantaneous.

Margin below +Perex SS; Dotecyldiphenyl ether disulfonic acid disodium 803 Na SO3Na that's all Applicant: Kao Soap Co., Ltd. 1”-1′・( Agent ga, yoi-a E-1-vote: 1...-1

Claims (1)

[Claims] 1. The following formula (1) and/or (II) 2 (wherein, R1 is a hydrocarbon group which may have a concave substituent group, R
2 represents a hydrogen atom or a methyl group, 2 represents an alkylene group having 2 to 4 carbon atoms, and M represents a monovalent or divalent cation. n represents a number from 0 to 100, and m represents an ion of M.) An alkenyl amber monoester salt represented by: 2. The following formula (1) and/or (ll)-2 (wherein, R1 represents a hydrocarbon group which may be a radical, R2 represents a hydrogen atom or a methyl group, and represents an alkylene group having 2 to 4 carbon atoms, M represents a 71-valent or divalent cation, n represents a positive value of 0 to 100, and m represents M
A reactive surfactant containing an alkenyl amber monoester salt represented by: 3. The following formula (1) and/or (II), 抛 (in the formula, R represents a hydrocarbon group which may have a substituent, R2 represents a hydrogen atom or a methyl group, and carbon An alkylene group of numbers 2 to 4, M represents 1111ti or a divalent cation, n represents an old number of 0 to 100,
(m indicates the ionic value of M) A molecular weight reforming agent containing an alkenyl succinic acid mononisnal salt represented by: