JP2837880B2 - Method for producing aqueous dispersion of long-chain alkyl graft polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an aqueous dispersion of a long-chain alkyl graft polymer, and more particularly to a method for producing a long-chain alkyl graft polymer by reacting a polyamine with an alkyl isocyanate. About.

The aqueous dispersion of the long-chain alkyl graft polymer of the present invention is used as a pressure-sensitive adhesive tape, a release agent used for back treatment of a sheet, and also used as a sizing agent, a surface treatment agent, a fluidizing agent for crude oil, and the like. it can.

[Prior Art] Conventionally, organic compounds such as polyvinyl alcohol-octadecyl isocyanate adduct (Japanese Patent Publication No. 29-7888) and polyethyleneimine-octadecyl isocyanate adduct (Japanese Patent Publication No. 40-17661) have been used as long-chain alkyl graft polymers. A production method in a solvent was known.

[Problems to be Solved by the Invention] These polymers are used by dissolving them in an organic solvent, and almost no long-chain alkyl graft polymers that can be used after dilution with water are known. Solvent-based polymers such as those described above require solvent recovery due to problems such as the deterioration of the working environment and pollution caused by organic solvents. May be changed to an aqueous type or a hot-melt type, and the demand for an aqueous dispersion of a long-chain alkyl graft polymer is increasing.

The present inventors have conducted repeated studies on a method for producing an aqueous dispersion of a long-chain alkyl graft polymer, and found that the reaction of a polyamine and an alkyl isocyanate in an emulsion state or a suspension state obtained by stirring with a homogenizer in water. As a result, it has been found that the object can be achieved very easily, and the present invention has been completed.

[Means for Solving the Problems] The present invention relates to a long chain grafted with an alkyl group having 8 to 30 carbon atoms obtained by reacting a polyamine with an alkyl isocyanate having an alkyl group having 8 to 30 carbon atoms. A method for producing an aqueous dispersion of an alkyl graft polymer, comprising reacting a polyamine and an alkyl isocyanate in an emulsion state or a suspension state obtained by stirring in water with a homogenizer. The present invention relates to a method for producing a dispersion.

Polyamine used in the present invention, polyethyleneimine, polyalkyleneimine such as polypropyleneimine, ethylenediamine, triethylenetetramine,
Polyalkylene polyamines such as tetraethylene pentamine, modified polyamines such as condensates of ethylenediamine and epichlorohydrin, water-soluble polymers such as polyvinylamine and polyallylamine, as long as they have active hydrogen that can react with isocyanate. The alkyl isocyanate used in (1) is a monovalent isocyanate having an alkyl group having 8 or more carbon atoms, and particularly, having 12 to 30 carbon atoms from the viewpoint of availability.
Those having an alkyl group are desirable. Examples thereof include long-chain alkyl isocyanates such as dodecyl isocyanate, tridecyl isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, nonadecyl isocyanate, and eicodecyl isocyanate.

By reacting the polyamine with the alkyl isocyanate, a long-chain alkyl graft polymer obtained by grafting an alkyl group having 8 to 30 carbon atoms (long-chain alkyl group) can be obtained.

In the present invention, a polyamine and an alkyl isocyanate are characterized by reacting in an emulsion state or a suspension state obtained by stirring in water with a homogenizer, for example, adding an alkyl isocyanate to an aqueous solution of a polyamine, The reaction proceeds in an emulsion state or a suspension state by vigorously stirring with an ominizer. At this time, in order for the reaction to proceed smoothly and completely, it is important to carry out the reaction in an emulsion state or a suspension state in which the alkyl isocyanate is sufficiently finely divided. Therefore, using a homogenizer which is a device having a strong shear force is used. It is necessary to perform stirring. The reaction is carried out at 0 ° C to 100 ° C, preferably at 5 ° C to 40 ° C. Heating more than necessary is not preferable because it promotes the reaction of the alkyl isocyanate with water.

At this time, the alkyl isocyanate can be added without being diluted, or can be dissolved in an organic solvent and diluted. When the melting point of the alkyl isocyanate is higher than the reaction temperature, it is preferable to dissolve the alkyl isocyanate in a solvent and carry out the reaction in order to carry out the reaction in a state where the alkyl isocyanate is sufficiently finely divided in water. As the solvent, those that do not freely mix with water are preferable.For example, aromatic solvents such as bezen, toluene, and xylene, and aliphatic solvents such as hexane, heptane, and octane, ethyl acetate, and butyl acetate are preferable. Ester solvents and the like can be used.

In dispersing the alkyl isocyanate in the aqueous solution of the polyamine, a surfactant may be used in order to sufficiently reduce the particle size of the alkyl isocyanate. There is no particular limitation on the surfactant used, but O / W
Those having a relatively high hydrophilicity capable of forming a type emulsion are preferred. Specific examples include nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene stearyl ether, anionic surfactants such as sodium lauryl sulfate and sodium polyoxyethylene nonylphenyl ether sulfate, and stearylamine acetate. And a cationic surfactant such as stearyltrimethylammonium chloride.

[Examples] The following examples specifically describe a method for producing a typical aqueous dispersion of a long-chain alkyl graft polymer, but are not limited thereto.

Example 1 2.6 g of polyethyleneimine (Nippon Shokubai SP-300 average molecular weight: 20,000) was completely dissolved in 75.0 g of water. To this, add 12.4 g of octadecyl isocyanate,
The mixture was stirred for 30 minutes with a homogenizer while keeping the temperature of the mixture to obtain an aqueous dispersion of polyethyleneimine-octadecyl isocyanate adduct.

The aqueous dispersion of octadecyl isocyanate was quantified by gas chromatography, and the selectivity of octadecyl isocyanate was determined by the following formula to be 96%.

ODI: octadecyl isocyanate Example 2 Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd.)
8.7 g of P-1000 active ingredient (30% by weight) and 3.0 g of a nonionic surfactant, polyoxyethylene nonylphenyl ether (HLB 17.5), were completely dissolved in 75.9 g of water. To this, add 12.4 g of octadecyl isocyanate,
The mixture was stirred for 30 minutes with a homogenizer while keeping the temperature of the mixture to obtain an aqueous dispersion of polyethyleneimine-octadecyl isocyanate adduct.

When the selectivity of octadecyl isocyanate was determined in the same manner as in Example 1, it was 95%.

Example 3 Polyethyleneimine (manufactured by Nippon Shokubai Chemical Industry Co., Ltd.)
2.6 g of SP-300 average molecular weight 20,000) and nonionic surfactant, polyoxyethylene nonyl phenyl ether (HL
B 17.5) 3.0 g was completely dissolved in 69.6 g of water. to this,
A solution prepared by dissolving 12.4 g of octadecyl isocyanate in 12.4 g of hexane was added, and the mixture was stirred with a homogenizer for 30 minutes while maintaining the temperature at 25 ° C to obtain an aqueous dispersion of polyethyleneimine-octadecyl isocyanate adduct.

When the selectivity of octadecyl isocyanate was determined in the same manner as in Example 1, it was 97%.

Example 4 Polyethyleneimine (manufactured by Nippon Shokubai Chemical Industry Co., Ltd.)
2.1 g of SP-018 (average molecular weight: 1800) and 4.8 g of a cationic surfactant, stearyltrimethylammonium chloride (solid content: 63% by weight) were completely dissolved in 67.3 g of water. To this, 12.9 g of octadecyl isocyanate was added to 12.
A solution dissolved in 9 g of ethyl acetate was added, and the mixture was stirred with a homogenizer for 30 minutes while maintaining the temperature at 25 ° C to obtain an aqueous dispersion of polyethyleneimine-octadecyl isocyanate adduct.

When the selectivity of octadecyl isocyanate was determined by the same method as in Example 1, it was 98%.

Example 5 2.3 g of tetraethylenepentamine and a nonionic surfactant, polyoxyethylene nonylphenyl ether (HL
B 17.5) 3.0 g was completely dissolved in 69.3 g of water. to this,
A solution obtained by dissolving 12.7 g of octadecyl isocyanate in 12.7 g of toluene was added, and the mixture was stirred for 30 minutes with a homogenizer while maintaining the temperature at 25 ° C. to obtain an aqueous dispersion of polyethyleneimine-octadecyl isocyanate adduct.

When the selectivity of octadecyl isocyanate was determined in the same manner as in Example 1, it was 98%.

Example 6 2.8 g of polyallylamine (average molecular weight 10,000) and 4.8 g of a cationic surfactant, stearyltrimethylammonium chloride (solid content 63% by weight) were completely dissolved in 68.0 g of water. A solution prepared by dissolving 12.2 g of octadecyl isocyanate in 12.2 g of toluene was added thereto, and the mixture was stirred for 30 minutes with a homogenizer while maintaining the temperature at 25 ° C., to obtain a polyallylamine-octatecyl isocyanate adduct aqueous dispersion.

When the selectivity of octadecyl isocyanate was determined in the same manner as in Example 1, it was 95%.

Comparative Example 1 Polyvinyl alcohol (average degree of polymerization 550 saponification degree 88.0
%) And a nonionic surfactant, polyoxyethylene nonylphenyl ether (HLB17.5) 3.0, were completely dissolved in 69.4 g of water. To this, 12.6 g of nooctadecyl isocyanate dissolved in 12.6 g of toluene was added, and 2
The mixture was stirred with a homogenizer for 30 minutes while maintaining the temperature at 5 ° C. to obtain an aqueous dispersion of an adduct of polyvinyl alcohol octadecyl isocyanate.

When the selectivity of octadecyl isocyanate was determined in the same manner as in Example 1, the result was 13%.

[Effects of the Invention] According to the present invention, a reaction between a polyamine and an isocyanate is carried out in water in an emulsion state or a suspension state, whereby the reaction is carried out quickly and with high selectivity, and the long-chain alkyl graft polymer is stabilized. Water dispersion can be obtained.

Continuation of the front page (56) References JP-A-1-135875 (JP, A) JP-A-61-90731 (JP, A) JP-A-52-12298 (JP, A) JP-B-40-17661 (JP, A) , B1) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 73/02

Claims (3)

(57) [Claims] An aqueous dispersion of a long-chain alkyl graft polymer obtained by reacting a polyamine with an alkyl isocyanate having an alkyl group having 8 to 30 carbon atoms and having an alkyl group having 8 to 30 carbon atoms grafted. A method for producing an aqueous dispersion of a long-chain alkyl graft polymer, comprising reacting a polyamine and an alkyl isocyanate in an emulsion state or a suspension state obtained by stirring in water with a homogenizer. 2. The method for producing an aqueous dispersion of a long-chain alkyl graft polymer according to claim 1, wherein the reaction is carried out in the presence of a surfactant. 3. The method for producing a long-chain alkyl graft polymer aqueous dispersion according to claim 1, wherein the polyamine is at least one selected from polyethyleneimine, polyvinylamine and polyallylamine.