KR900005402B1 - Process for the preparation of viscosity regulator - Google Patents

Abstract

A viscosity regulator is prepd. by reacting organic acid mixt. of 1 mol monoatomic organic acid and 0.05-0.4 mol diatomic organic fatty acid with 0.01-0.1 mol copolymer of styrene and maleic anhydride at 150-170 deg.C, reacting the mixt. with 0.5050.95 mol diatomic amine cpd. at 180-200 deg.C to produce ester amide wax, crushing the wax to be 50 micrometer or less, and swelling and aging the crushed wax in the mixt. solvent comprising organic alcohol and aromatic solvent. The regulator has excellent heal-stability and thixotropy.

Description

Viscoelastic modifier manufacturing method

The present invention relates to a method for preparing a viscoelastic modifier (Thixotropic Agent or Reology Modifier) based on the preparation of ester amide wax used to control the flow characteristics of a fluid containing a water-insoluble suspension or fine solid particles.

In general, the speed at which solid particles settle in the fluid system can be expressed by the formula of Stoke.

That is, in order to reduce the settling speed, it can be solved by reducing the radius of the dispersed particles, decreasing the density difference between the fluid and the particles, or increasing the viscosity of the fluid. The high viscosity at the time of not only poor workability, but also has a disadvantage in that a smooth surface is not obtained because of poor leveling.

Although the general fluid maintains a constant viscosity, the viscoelastic modifier has a gel state when stationary, and when stress or shear stress is applied from the outside, it changes from a gel state to a sol state and has a lower viscosity than when stationary. When the stress is reduced and the external stress is removed again, the gel is reduced from the sol state to the gel state, and the reversible change of the gel and the sol where the viscosity is restored is possible.

This characteristic is called thixotropy, and the Korean Industrial Standard (KS M5001) states that it is a reversible property of a colloidal dispersion which becomes sol phase when stirred at a constant temperature and gel when left standing.

Viscoelasticity modifiers are added to paints, varnishes, printing inks, adhesives, laminates, enamels, etc. to reduce the viscosity during operation to improve flow characteristics and to suppress the flowability of fluids after operation. It has the property of preventing sedimentation of solid particles during storage.

Studies on viscoelastic modulators having the properties of thixotropy have been continued, but the conventional viscoelastic modulators have the following disadvantages.

(1) Metal salts, such as aluminum stearate, are easily precipitated in polar solvents such as water or alcohol, or sediment nuclei are generated, resulting in poor water resistance and poor gloss. (2) The montmorillonite derivatives are prone to poor conditions during swelling and dispersion, and have the disadvantage of reducing viscoelastic properties. (3) viscoelasticity regulators of fatty acid type, gloss reduction and precipitation nuclei occur when using pigments such as zinc oxide, chrome yellow, calcium carbonate, etc. (4) viscoelasticity regulators based on hydrogenated castor oil prevent flow Good stability but poor thermal stability, so precipitation nucleus occurs even at 50 ℃ or 40 ℃, so it is difficult to control temperature when dispersing such as milling or grinding. (5) Emulsifiable polyethylene wax prevents flow and precipitate nuclei. The inhibitory effect is good, but there is a disadvantage that the flow prevention effect does not occur immediately after removing external stress, and there is a disadvantage that greatly reduces the gloss of the coating film during the painting work.

In US Patent No. 3,937,678, there was a method of melt-mixing an emulsifiable polyethylene wax in amide wax, and US Patent No. 4,128,436 had a method of melt-mixing castor oil added with hydrogen to amide wax.

The above technique is unsatisfactory in heat stability and viscoelastic properties, and there is a process of melt mixing after preparing the amide wax.

The present invention is to solve the above problems, after the first reaction of a copolymer of styrene and maleic anhydride to a monovalent organic acid having a hydroxyl group or a mixture of these organic acids and divalent organic fatty acids, an aliphatic containing a primary amine group at both ends of the molecule By preparing the amide wax having an ester group by reacting the amine compound and swelling and swelling it after crushing, it has better heat stability than the existing amide wax-based viscoelasticity control agent, less viscosity change with temperature during storage, and good flow prevention effect when standing. In addition, it was able to solve the coagulation (hard cake formation phenomenon) that solid particles are settled and solidified during storage.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT In detail, the organic acid mixture in which 1 mol of monovalent organic acid or 1 mol of monovalent organic acid and 0.05-0.4 mol of divalent organic fatty acid is mixed is first reacted with 0.01 to 0.1 mol of copolymer of styrene and maleic anhydride. In the second reaction, 0.55-0.95 mol of a divalent amine compound was reacted to prepare an ester amide wax (Ester Amid Wax).

The first reaction is carried out at a temperature of 150 ~ 170 ℃, the reaction completion point is determined in the state that the acid anhydride group (anhydride group) is completely disappeared, the second reaction is carried out at a temperature of 180 ~ 200 ℃.

The reaction catalysts usable in the secondary reaction are tetraspropyl zirconate, tetrapropyl titanate, titanium acrylacetonate and titanium polyhydroxy stearate. Boric acid, alumina, and the like are useful.

It is important that the final reaction product, ester amide wax, is reacted to maintain the acid and amine numbers below 10.

If the acid value and the amine value are too high (10 or more), there are many unreacted substances, so that the thermal stability and cake formation are severely adversely affected. In the state where the acid value and the amine value are too low, the performance of thixotropy is reduced.

As the monovalent organic acid in the first reaction, 9-hydroxystearic acid, 12-hydroxystearic acid, etc. may be used, and sebacic acid may be used as a divalent organic acid. Sebacic Acid, Adipic Acid, Succinic Acid, Hydrogenated Dimer Acid, 1, 12-Dodecanedioic Acid, Glutar Acids (Glutaric Acid) and the like can be used.

As a copolymer (SMA) of styrene and maleic anhydride, the horizontal group has a molecular weight of 1600 to 2300, a melting point of 55 to 170 ° C, and an acid value of 105 to 480.

Since ester amide wax using the copolymer of styrene and maleic anhydride contains aromatic group in the molecule, it shows high thermal stability and improves affinity with aromatic solvent to facilitate dispersion, swelling and ripening. It contributes well to the flow prevention effect, and overcomes the disadvantage of solid particles settling and condensation during long-term storage.

As the divalent amine compound in the secondary reaction, ethylenediamine, tetramethylene dimin, hexamethylenediamine, octamethylenediamine, decadiamine, or the like can be used alone or in combination.

Viscoelasticity regulator is prepared by pulverizing the ester amide wax prepared by the above method to 50㎛ or less and then swelling in a mixed solvent consisting of an aromatic solvent (B.T.X-based solvent) and organic alcohol.

That is, 1) 10 to 30 parts of ester amide wax ground product having a maximum particle diameter of 50 μm, and 2) 70 to 90 parts of a mixed solvent composed of an aromatic solvent and an organic alcohol, followed by swelling and swelling to paste. Manufacture.

As the aromatic solvent (B.T.X-based) in 2), benzene, toluene, ortho-xylene (o-Xylene), para-xylene, and metha xylene can be used, and they can also be used as a mixed solvent in which these are mixed.

As the organic alcohol, methanol, ethanol, ethylene glycol, n-propanalcohol, n-butanol, isopropanol, isobutanol, octanol, and the like can be used. It can also be used as alcohol, and it is used in 5 to 30 parts with respect to 100 parts of mixed solvent.

At this time, if the content of organic alcohol is excessively used in the water-insoluble fluid system containing the water-insoluble suspension or fine solid particles, the viscoelasticity modulator after swelling maturation forms an aggregate of swelling bodies with each other during long-term storage. Condensation has a side effect and the flow prevention effect is lowered.

Even when the pulverized particles of 1) are large, it is difficult to form a swelling body, and it is difficult to form a uniform surface because the surface is coarse due to the occurrence of side effects and drying.

In the following Examples will be described a specific manufacturing method and effect of the present invention.

Example 1

In a reactor equipped with a dehydration device, 1 mole of 12-hydroxystearic acid and 0.05 mole of SMA copolymer having a molecular weight of 1600 and an acid value of 480 were added and the temperature was increased. After melting, the reaction was carried out at 170 ° C. until all the acid anhydrides disappeared. After dropping 0.525 mol (Ethylene diamine) over 1 hour, the reaction was terminated by raising the temperature to 200 ° C.

The reaction is carried out in the presence of nitrogen, but at the end of the reaction by vacuum at 100mmHg to completely remove the unreacted matter and water.

The reaction product (acid value 3, amine value 1) was cooled to 20 parts of pulverized product with 50 µm or less of 60 parts of xylene, 5 parts of ethylene glycol, and 15 parts of ethanol, mixed well, and then swelled to form a viscoelastic regulator. Got.

Example 2

When 1 mole of 9-hydroxystearic acid, 0.4 mole of sebacic acid, 2500 mole of molecular weight, and 0.01 mole of SMA copolymer having an acid value of 175 are added to the reactor and melted at 150 ° C. React until.

Then, 0.905 mole of hexamethylenediamine was added thereto, followed by reaction at 180 ° C. for 2 hours, followed by reaction at 200 ° C. until the acid value became 7 or less, and then maintained under 100 mmHg vacuum for 30 minutes to remove moisture and unreacted substances. After the product of 6 was obtained, the product was cooled, and 5 parts of n-butanol and 75 parts of toluene were added to 20 parts of the reaction pulverized product having a particle size of 50 µm or less.

Example 3

0.1 mol of SAM copolymer having a molecular weight of 1900 and an acid value of 275 was added to 1 mol of 12-hydroxystearic acid, and nitrogen was injected into the reactor. The temperature was raised to 150 µm, and after stirring, all the acid anhydrides were consumed. 0.4 mole of diamine and 0.15 mole of hexamethylenediamine were added to terminate the reaction at 200 ° C. to obtain a product having an acid value of 5 and an amine value of 3. The product was then pulverized to 20 parts of pulverized product having a maximum particle size not exceeding 50 μm. 5 parts, 10 parts of ethanol, 60 parts of toluene, and 5 parts of benzene were added to obtain a viscoelastic modifier mixed and swelled.

Comparative Example 1

0.5 part of ethylenediamine is reacted with 1 mole of 12-hydroxystearic acid at 200 ° C to cool down and pulverize the reaction product having an acid value of 4 or less and an amine value of 3 or less. 60 parts of xylene, 5 parts of ethylene glycol, and 15 parts of ethanol were mixed well to obtain a viscoelastic regulator obtained by swelling.

Comparative Example 2

1 mole of 12-hydroxystearic acid was reacted at a ratio of 0.4 mole of sebacic acid and 0.9 mole of hexamethylenediamine to obtain a product having an acid value of 7, an amine value of 5, and then 20 parts of a pulverized product obtained by grinding the amide wax to 50 μm or less. 5 parts of normal butyl alcohol and 75 parts of toluene were mixed well, and the viscoelasticity regulator obtained by swelling was obtained.

Comparative Example 3

The viscoelasticity modifier was obtained by making it swell by making 80 parts of xylene into 20 parts of amide wax crushed products similar to the comparative example 2.

[Application Example]

Chlorinated Rubber Paint

1.Chlorinated rubber (superchlon # 507, Sanyo Kokusakusa product: 20 parts

2. Chlorinated Paraffind (45% Cl): 9 parts

3.Typeque R-820 (manufactured by Chihara Sanyo): 30 parts

4. Liquid epoxy resin (YD 128, manufactured by Kukdo Chemical Co., Ltd.): 40 parts

5. Solvent (Xylene): 40 parts

3.5 parts of the viscoelastic modifiers prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 were added to 96.5 parts of the paint composition as described above, followed by dispersion at 2000 rpm for 30 minutes using a high speed dissolver. After comparing the following physical properties.

As a result of comparing the product of the present invention and the conventional product according to the application example described above, the product of the present invention has excellent thermal stability, excellent thixotropy, exhibits viscoelastic properties, and particles such as pigments are precipitated and condensed. The shortcomings were solved.

Claims (6)

1 mole of stearic acid containing a hydroxyl group or a mixture of 0.05 to 0.4 mole of aliphatic diacid is reacted with 0.01 to 0.1 mole of copolymer (SMA) of styrene and maleic anhydride, followed by 0.505 to 0.95 mole of aliphatic amine A method of producing an ester amide wax having an acid value of 10 or less and an amine value of 10 or less by reacting. The method of claim 1, wherein stearic acid is 9-Hydroxy stearic acid, 12-Hydroxy stearic acid, aliphatic diacid is an organic acid having 2 to 8 carbon atoms, aliphatic Amine is a method for producing ester amide wax, characterized in that the divalent aliphatic amine. The method of claim 1, wherein the copolymer of styrene and maleic anhydride (SMA) has a molecular weight of 1600 ~ 2300, melting point 55 ~ 170 ℃, acid value 105 ~ 480, characterized in that the ester amide wax production method. A method for preparing a viscoelastic modifier prepared by kneading a paste of 10 to 30 parts by weight of a pulverized product obtained by pulverizing the ester amide wax of claim 1 in 70 to 90 parts by weight of a mixed solution of an alcohol and an organic solvent. The method of producing a viscoelastic modifier according to claim 4, wherein the mixed solution of alcohol and organic solvent comprises 95 to 70 parts by weight of organic solvent and 5 to 30 parts by weight of alcohol. The organic solvent according to claim 5, wherein the aromatic (BTX) organic solvent is a mixture of benzene, toluene, o, m, and p-xylene (alone) or two or more kinds, and alcohols are 1 to 10 carbon atoms. A method for producing a viscoelastic modifier, characterized in that it is used alone or in combination of two or more as a secondary organic alcohol.