JPS5919729B2 - Amine oxide group-containing polymer surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an amine oxide group-containing polymeric surfactant.

For example, the amine oxide group-containing low-molecular compound has the general formula R1
R2R3N→O (in the formula, R1, R2, and R3 represent an alkyl group.

The arrow indicates a coordinate bond), and it is useful as a detergent and a surfactant. A well-known manufacturing method includes oxidizing a tertiary amine with an oxidizing agent such as a persulfate or Fenton's reagent. However, little is known about polymeric surfactants containing amine oxide groups. The present inventors have arrived at the present invention as a result of repeated research on polymeric surfactants containing amine oxide groups.

That is, the present invention provides N.N dimethylaminostyrene, N
・N-dimethylaminomethylstyrene, N,N-dimethylaminoethyl isopropene, N・N-dimethylaminoethyl methacrylate, N・N-diethylaminopropyl methacrylate, N・N-diethylaminoethyl acrylate, N-(N' ・N '-dimethylaminoethyl)acrylamide, vinyl N.N-dimethylaminopropionate, and N.N-dimethylaminoethyl(polyethoxy)acrylate, or a polymer containing the monomer and styrene. A copolymer with a monomer (B) selected from the group consisting of compounds, vinyl alcohol fatty acid esters, (meth)acrylic acid alkyl esters, hydroxyalkyl (meth)acrylates, (meth)acrylamides, fatty acid vinyl ethers, and acrylonitrile. General formula (where R is hydrogen or methyl group;
R' and w are each independently an alkyl group having 1 to 4 carbon atoms;
This is an amine oxide group-containing polymeric surfactant obtained by oxidizing a polymeric compound having a structural unit represented by the following formula: X is a divalent bonding group; n is O or the number 1.

To explain the compound represented by the general formula used in the present invention, examples of X in the general formula include -COOA-,
-00C-A-, -CONHA- and -COO(AO
) p-A-, where A is a lower alkylene group having 1 to 4 carbon atoms, p is a number from 1 to 10, and the benzene ring is 1
It may have the above substituents. Examples of compounds represented by the general formula include those represented by the formula, where R is hydrogen or a methyl group; K, . Bi is each independently an alkyl group having 1 to 4 carbon atoms; a is O or 1
, b is a number from 0 to 4, c is a number from 1 to 3, p is a number from 1 to 10
is the number of

These structures are N-N-dimethylaminostyrene, N-
N-dimethylaminomethylstyrene, N-N-dimethylaminoethyl isopropene, N-N-dimethylaminoethyl methacrylate, N-N-diethylaminopropyl methacrylate, N-N-diethylaminoethyl acrylate, N-(N'・N- It is obtained from polymers and copolymers of monomer (4) selected from the group consisting of dimethylaminoethyl)acrylamide, vinyl N-N-dimethylaminopropionate, and N-N-dimethylaminoethyl(polyethoxy)acrylate. Monomers that can be copolymerized with the monomer include styrene, vinyl alcohol fatty acid ester, (meth)acrylic acid alkyl ester, hydroxyalkyl (meth)acrylate, (meth)acrylamide, fatty acid vinyl ether, and acrylonitrile. is the monomer of choice. Examples of the oxidizing agent used for oxidation in the present invention include ammonium persulfate, sodium persulfate, Fenton's reagent, hydrogen peroxide, and peracetic acid.

In the method for producing a surfactant of the present invention, the molar ratio of the oxidizing agent to the tertiary amino group in the compound represented by the general formula is 0.00.
1 to 2.0, preferably 0.5 to 1.5, the reaction temperature is 0 to 200°C, preferably 20 to 100°C, and the pressure may be increased, but normal pressure is preferable.

Any solvent may be used as long as it does not oxidize itself, such as water,
Examples include hydrocarbons such as toluene, xylene, hexane, and cyclohexane, and esters such as methyl acetate and ethyl acetate. The amine oxide group-containing polymeric surfactant of the present invention is useful as a surfactant and a cleaning agent, and can also be used as a conductive agent, an antistatic agent, a lubricating oil additive, etc. Widely used,
It also has good compatibility with resins. The present invention will be explained below with reference to Examples.

Example 1 Poly-N-N-diethylaminoethyl methacrylate (
Dissolve 18.5 parts (molecular weight approximately 15,000) in 50 parts of xylene and charge into a 3-tube flask equipped with a stirrer, a thermometer lid* and a cooling tube, and add 13.6 parts of 30% hydrogen peroxide solution at room temperature. Add.

The temperature was raised to 60 to 70° C. while stirring, and the reaction was carried out at the same temperature for 3 hours to obtain a corresponding polymeric surfactant having an amine oxide group (referred to as Compound Taki 1 of the present invention). This product was water-soluble, N→O absorption was observed in the infrared absorption spectrum, and the conversion rate to amine oxide was 75%. Example 2 Poly 4-(N-N-dimethylaminomethyl)styrene (
Disperse 16.2 parts (molecular weight 5000) in 50 parts of water,
While stirring, 13.6 parts of 30% hydrogen peroxide solution was added dropwise at room temperature over 30 minutes.

After the dropwise addition was completed, the temperature was raised to 60° C. and the reaction was carried out for 7 hours, resulting in a uniform system 5. After the reaction was completed, an amine oxide group-containing polymeric surfactant (referred to as Compound Taki 2 of the present invention) was obtained. When analyzed in the same manner as in Example 1, this product was water-soluble, and the infrared absorption spectrum showed N→0 absorption, and the conversion rate to amine oxide was 82% (9%). Example 3 Table 1 shows the results of reacting a polymer compound dissolved or dispersed in a solvent with an oxidizing agent in the same manner as in Example 1.

Example 4 (Physical property test) Table 2 shows the test results for foaming power and surface tension of various ato group-containing polymeric surfactants synthesized in Examples 1 to 3.

Claims (1)

[Claims] 1 N·N-dimethylaminostyrene, N·N-dimethylaminomethylstyrene, N·N-dimethylaminoethyl isopropene, N·N dimethylaminoethyl methacrylate, N·N diethylaminopropyl methacrylate, N・N-diethylaminoethyl acrylate, N-(
N'/N'-dimethylaminoethyl)acrylamide,
Vinyl N・N-dimethylaminopropionate, N・N-
A polymer of monomer (A) selected from the group consisting of dimethylaminoethyl (polyethoxy)acrylate, or a polymer of monomer (A) and styrene, fatty acid ester of vinyl alcohol, alkyl (meth)acrylate ester, hydroxyalkyl ( It is a copolymer with a monomer (B) selected from the group consisting of meth)acrylate, (meth)acrylamide, and acrylonitrile, and has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R is hydrogen or methyl group; R ', R'' are each independently an alkyl group having 1 to 4 carbon atoms; X is a divalent bonding group; n is a number of 0 or 1). Group-containing polymeric surfactant.