JPS6078947A - Quaternary ammonium salt and reactive surfactant and high polymer modifier containing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the following formula (1) containing a (meth)allyl group as a radical merging group (wherein, R1 has 8 to 220 carbon atoms and may have a pupil substituent group).
(R2 and R3 are alkyl groups having 1 to 3 carbon atoms, R4 is a hydrogen atom or a methyl group, and Xo is a monovalent anion) The present invention relates to a salt, a reactive surfactant containing the salt, and a molecule-modifying agent.

Conventionally, emulsion polymerization reactions have been carried out using non-reactive surfactants. However, in the emulsion removed by this method, the surfactant remains locally condensed without being mixed with the polymer, so in the process of making a film from the polymer, the surfactant remains in the film. This is due to the fact that a homogeneous polymerized film is obtained.
'il [was. It has been known that this non-uniformity of the polymer film has a negative effect on various properties such as dyeing properties, iY anti-rust properties, weather resistance, and mulberry resistance.

In order to overcome this shortcoming, in recent years, the molecule has both a group that has surface-active ability and a group that cools polymerization, and instead of acting as an emulsifier for the monomer, it has been developed that the polymer gradually forms during polymerization. Reactive surfactants that are being incorporated into the world are now being used.

As a result of extensive research into reactive surfactants, the present inventors discovered that (meta) as a radically polymerizable group in the molecule.
The quaternary ammonium salt represented by the above formula (1) having a furyl group is a useful reactive surfactant, that is, the substance contains a hydrocarbon group which is a hydrophobic group and a hydrophilic group. Since there is a quaternary ammonium group, it is possible to change the hydrophilic and lipophilic j□ lances depending on the 7-mer to make emulsification double in the most suitable condition.
631 heading, eh. : In addition, when the quaternary ammonium clay is used in a larger amount than the reactive surfactant used in conventional emulsion polymerization, it is possible to impart hydrophilicity to a hydrophobic resin, It has been found that it is also useful as a modifying agent.

The present invention is based on the above findings, and therefore, an object of the present invention is to provide a novel quaternary ammonium salt represented by the above formula (1), a reactive surfactant containing the same, and a polymer modified This is to provide medication for the treatment.

The compounds represented by the formulas of the present invention are prepared, for example, according to the following formulas.

(B (IV) person 艷ciN, -cncnllocn, c=cn, (V) (1
) (In the formula, R1, R2%, R3, R4 and IV) with 7lylglycisol ether (V) to form the compound of the present invention (
1) is manufactured.

The starting material, tertiary a?, represented by the formula (...)? is,
When R2 and R3 are methyl groups, they are produced by the so-called leucardobaraton reaction, that is, by reductive alkylation of a primary amine with formic acid and formaldehyde.

For example, if r-decylamine is used as the primary amine, dimethyldodecylamine will be obtained, and if octadecylamine is used, dimethyloctadecylamine will be obtained.

The acids represented by the formula (see 1) are not specified and can be used in an anhydrous state or an aqueous state. Examples of these acids include hydrogen chloride, hydrogen bromide, and hydrogen fluoride. , hydrogen iodide, perchloric acid, nitric acid, inorganic acids such as L acid, 1.Q radluene sulfonic acid, monomethyl sulfonic acid, mo/x-1-l iL [, methanesulfone 1 section,] Organic compounds such as methanesulfone #, O'+1, zolopionic acid, and trifluoroacetic acid can be used.

In the above reaction, a solvent may or may not be used, but it is preferable to use a bath medium that dissolves the salt (IV) produced. Now, let's take the example of ethanol, which is alcoholic alcohol.
Ketones such as acetone and methyl ethyl ketone; ethers such as dioxane, ethylene glycol and dimethyl ether can be used.

The reaction between salt (1!/) and allylglycisol ether (■) can be carried out by, for example, adding 30 to 160
C., preferably 60 to 100.degree. C., and allylglycisol ether M is added dropwise thereto, or both are charged at once and reacted.

At this time, a solvent may or may not be used, but it is preferable to use the organic solvent used in the above neutralization reaction. The reaction molar ratio is suitably 1 to 2 moles of sialylglycisol ether (v) per 1 mole of salt (IV), particularly 1.0
~1.3 mol is preferred.

Ethylenically unsaturated polymers that can be emulsion polymerized using the compound (1) of the present invention thus obtained as a reactive surfactant include styrene K4, vinyl esters, acrylic esters, and methacrylic acid. Esters, acrylic acid, methacrylic acid, croton (narrow α,
β-unsaturated carbon @ or in situ; acrylamide,
α, β unsaturated amides such as methacrylamide, N-methylbucryl 7mide, and N-methylol acrylamide; conjugated dienes such as acrylonitrile-tacrylonitrile, vinyl thickening, vinylidene chloride, ethylene, α-olefin, and putazoene; Alkyl vinyl ether'Jl
+, alkyl vinyl ketone m, jll [li water, maleic acid, maleic esters, itaconic esters, etc. are included. Also included are crosslinkable divinyl compounds such as divinylbenzene, ethylene glycol dimethacrylate, and methylene bisacrylamide.

The reaction temperature when carrying out emulsion polymerization using the compound q) of the present invention as a reactive surfactant is 0°C to 100°C, preferably 20°C to 90°C, and polymerization with a polymerizer initiator in an inert gas. Modifiers can be added and polymerized.

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. However, these methods 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 of the known water-soluble radical polymerization initiators can be used.
? C. Toe is inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, known water-soluble organic peroxides, or these peroxides with sodium hydrogen suboxide,
This is a redox polymerization initiator system that uses a reducing sulfoxy compound such as sodium thiomril and ferrous sulfate.

Use of the compound of the present invention (li as a reactive surfactant)
The amount of li can be varied depending on the type of polymer, monomer composition, purpose, performance of water spraying, etc.
When producing a hydrophobic polymer for the purpose of dyeing properties, antistatic properties, etc., the compound (I) of the present invention is usually contained in the copolymer in an amount of 011 to 40% by weight (hereinafter simply indicated by 9)1, It is preferable that 0.2 to 3 ON is contained in the compound of the present invention.Furthermore, the compound of the present invention can also be used as a polymer modifier. That is, when used as the above-mentioned reactive field Wri activator, a hydrophilic polymer is mixed from monomers that produce a hydrophobic polymer by blending it in the co-monomer so that the ratio is 10 to 8096, preferably 20 to 60X. Coalescence (e.g. swellable resin)
C, □ By using the reactive surfactant of the present invention, it is possible to impart excellent dyeing properties, antistatic properties, water resistance, hydrophilicity, water retention properties, etc. to various polymers. That is, in the polymer produced using the reactive surfactant of the present invention, after copolymerization, the hydrophilic groups resulting from the copolymerized surfactant are uniformly dispersed, so that the above properties are improved, especially permanently. It is possible to improve antistatic properties, antifogging properties, and pigment miscibility.

In addition, even if the reactive surfactant of the present invention is used in large quantities in an emulsion polymerization system for the purpose of modifying the polymer, it remains as it is in the polymer due to its good copolymerizability. There is no.

Therefore, polymer modifiers made of known monomers containing carboxyl groups or sulfo groups, such as sodium (meth)acrylate, sodium styrene sulfonate,
Sodium (meth)allylsulfonate, sodium 2-acrylamido 2-methylpronoqsulfonate, (meth)acryloyloxyethyltrimethylammonium salts, 3-(meth)acryloyloxy-2-hydroxypropyltrimethylammonium salt m, 3-(meth)acryloyloxyethyltrimethylammonium salts )
Like allyloxy-2-hydroxy 7P dibyltrimethylammonium salts, a water-soluble mono[j complex is formed,
There is no possibility that the water resistance of m-fat will be realized.

Furthermore, the polymer modification method of the present invention can be used not only in emulsion polymerization systems, but also in suspension polymerization systems, bulk polymerization systems, and solution polymerization systems using solvents. This is because the polymer modifying agent of the present invention has a wide solubility not only in water but also in hydrophobic solvents and hydrophobic monomers.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A 1 t glass reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a temperature needle was heated with a tertiary amine.
Rylzomethylamine 2'17.6f (1 mol) and Impronoqnol 500t are charged, and 359 hydrochloric acid 104.2F is added dropwise over 15 minutes while keeping the temperature at 30°C in a water bath. Well, it turned out to be Luglycisol Ether 125.6f (
After that, isoprono-9-nol was distilled off under reduced pressure, and the oil-like residue solidified as the system cooled. did. When the reaction was completed by applying a quantitative method using a cationic interface and a surfactant using prolphenol blue as an indicator, the reaction value was 96y6. Further, the residue was recrystallized from acetone to obtain a white crystalline powder.The white crystalline powder was obtained by nuclear magnetic resonance (
Analysis of NMR) spectrum and infrared absorption (IR) spectrum confirmed that it was 3-allyloxy-2-hydroxyzolobylzomethylstearylammonitum chloride represented by the following formula.

(a) ” II-NMR (δkn ppm s C
C4, TM8 internal standard) 0.86 (3H*t) C)
Ig-(CH*)+s-1,00~1.50 (32H,
Broad) C) 13-(c 伽) 16-3.10~4.
60 (16H, m) C: 弗4.85~5-43 (2)i #m) -0-C
lI2- CH-CH25,53-6.23 (IJl,
m) -0-CH2-C ha=eH2(b) 13C-N
MR (δin ppm, CDCl2. TM8 internal standard) Fn3 1:14.1 (ql 2:22.7(t) 3:31.
9(t)4:29,? (t) 5: 26.3(t)
6: 65.5 (t)? : 52.6 (ql 8
: 66.4<t) 9 : 64.3(a) 10 near 2.3D) 11 near 2.3 (tl 12:134.4
(d113: 117.1(t) d: 2-breath line, t: 3-fold condensation, q: 4-fold line (e) IR (crn-” I KBr method), 3700
~3100,2940.2870.1720.1640
゜1550.1460.1380,1320.1300
, 1170°940.810,755.710 Examples 2 to 5 Example 1 except that the stearylzomethylamine used in Example 1 was replaced with the amines and acids shown in Table 1 below.
The reaction was carried out in the same manner as above, and the reaction product was recrystallized from Fushitaton to obtain a white powder. The white powder was analyzed by NMR and IR in the same manner as in Example 1, and it was confirmed that these were compounds having the structures shown in Table 2. Also shown are the reactions that occurred.

Table 1 Example 6 Using the reactive surfactant obtained in Example 1, a monomer emulsion was prepared as follows. i.e. a stirrer,
Put 50 f of water into a reactor equipped with a thermometer, reflux condenser, nitrogen inlet, and dripper, replace the system with renal gas, and raise the temperature to 75°C. Next, 3-pryloxy-2-hydroxyterovir dimethylstepril and ammonium chloride, which is the reactive surfactant 11J obtained in Example 1, are added in the amounts shown in the third passage. On the other hand, methyl methacrylate (V-) 48f and butyl acrylate were added to a water bath solution in which 0.5f of 2.2-azobis<2-yomicip...qn) dihydrochloride was dissolved in 1010□f of water as a polymerization initiator. )52
9 and shake to make a seven-mer emulsion. Then, the monomer emulsion is placed in a dropping funnel and dripped into the stirred reaction vessel over a period of 2 hours. After the dropwise addition was completed, stirring was continued for another 2 hours at 75°C to obtain the polymer emulsion shown in Table 3.

Moreover, R1 of the above polymer emulsion! ! A polymer emulsion was subjected to FAN as a comparative product in the same manner as described above except that trimethylstearylammonium chloride was used in place of 3-hydroxy-2-hydroxyprobylzometelstearylammonium chloride in the manufacturing method. It should be noted that 3-pyryl-7-2-hydroxyzolobyltrimethylammonium chloride could not be obtained in place of 3-hydroxy-2-hydroxyzolobylzomethylstefuryl ammonium.

Regarding the polymer emulsion thus obtained, It's a fake. Show the ice on the third coat.

[Measurement/evaluation method]

Synthesis stability: Filter through 100 mesh gold FF13, wash the filtration residue with water, dry at 105±2°C for 12 hours, and remove acid. The drying resistance U is increased by the resistance 9 for the monomer used.

Mechanical stability: Determined in a Marlon tester under a load of 10F-2, with a weight of 90% for the latex solids content of the agglomerate formed after stirring for 5 minutes.

Water resistance: Measured based on the standard of time for whitening using the submersion method of approximately 0.3 mm membrane: 1 day or more, 021 hours or more, ×: less than 1 hour, xx: 1 yen hour. .

Heat resistance: Judgment was made based on the change in appearance after heating at 120°C for 24 hours. O: Appearance is the same as before heating, o: +
Slightly colored in. ×: Colored to the extent that it can be distinguished from the color.

The following content: 111 In the product of the present invention, 3-furyloxy-2-hydroxy f
a Pyrzomethylstearyl hummonium chloride, the comparative product is trimethylstearyl hummonium chloride Example 7 Among the various polymer emulsions obtained in Example 6, the present invention product (c) or the comparative product (2) was It was coated on a drying test paper using a No. 7 bricator and dried at 50°C for 1 hour to obtain a coating film with a thickness of about 8P.Then, the rough film was coated in an atmosphere of 20°C and 50% relative humidity. The blush resistance of 611j was measured using the following method.After the completion of the 611j test, the surface of the coating film was wiped twice with water-containing tissue paper (tissue paper, e), and dried at 50°C for 10 minutes. Then, the right surface resistance was measured on the same edge as above.

Thereafter, this operation was repeated 2 to 5 times. The results are shown in Figure 1.

〔Measuring method〕

The surface resistance is measured using the room temperature measurement box model p-601 (
(manufactured by Kawaguchi Denki Seisaku Qr) K-1 resistance meter model 4329 (manufactured by Hewlett No. Q Card Co., Ltd.)
It was carried out using a pith connected to the

As shown in Figure 1, it can be seen that the product of the present invention has water-intoxicating properties.

[Brief explanation of the drawing]

Figure 1 The bottom surface of the polymer emulsion coating film by wiping with water [i! ! FIG. 1 is a drawing showing resistance changes.

Claims (1)

[Claims] 1. R, OR in the following formula (wherein, R8 represents a hydrocarbon group having 8 to 22 carbon atoms which may have a substituent, and R1 and R1 represent a hydrocarbon group having 1 to 3 carbon atoms). Alkyl group ?1IR4 represents a hydrogen atom or a methyl group, Xo
indicates a monovalent ion) A quaternary ammonium salt represented by QyF/7-1:f'1i1 (wherein, R1 is a hydrocarbon group having 8 to 22 carbon atoms which may have a substituent, R2 and R3 are an alkyl group having 1 to 3 carbon atoms, and R4 is Reaction a containing a quaternary heptammonium salt represented by (representing a hydrogen atom or a methyl group, and xo represents a monovalent anion)
surfactant. 3. The following formula (1) (wherein, RX is tM, carbon number 8 to 2 which may have a substituent
2 is a hydrocarbon group, R2 and R3 are an alkyl group having 1 to 3 carbon atoms, R4 is a hydrogen atom or a methyl group, and
represents a monovalent anion) A polymer modifying agent containing a quaternary ammonium salt represented by: