KR20130057579A - Polyoxyethylene-polyoxypropylene block or random addition ether of higher alcohol - Google Patents

Abstract

PURPOSE: A copolymer is provided to obtain low bubble performance by introducing a propylene oxide into an alcohol ethylene oxide, and to improve cleaning force and exterior appearance. CONSTITUTION: A copolymer is manufactured by a basic catalyst, and is formed by combining an ethylene oxide-propylene oxide with C8-18 higher alcohol. A manufacturing method of the copolymer comprises: a step of mixing 1 part by mole of C8-18 higher alcohol and 0.001-0.1 parts by mole of base catalyst; a step of adding 5-12 parts by mole of ethylene oxide and 2-7 parts by mole of propylene oxide into the higher alcohol, and aging the same; and a step of injecting a decatalysting agent to remove the basic catalyst.

Description

Higher alcohol ethylene oxide-propylene oxide blocks or random copolymers and preparation method thereof {POLYOXYETHYLENE-POLYOXYPROPYLENE BLOCK OR RANDOM ADDITION ETHER OF HIGHER ALCOHOL}

The present invention relates to a higher alcohol ethylene oxide-propylene oxide block or random copolymer and a method for producing the same, and more particularly to a higher alcohol ethylene oxide-propylene oxide block or random copolymer for use as a surfactant and a method for producing the same. It is about.

Recently, the importance of nonionic surfactants, which are widely used as laundry detergents, dishwasher detergents, industrial detergents, and emulsifiers, is increasing in terms of environmental protection. Nonionic surfactants have several advantages over ionic surfactants. The anionic surfactants belonging to the ionic surfactants form a complex salt when used in combination with the cationic surfactants, resulting in poor compatibility, but the nonionic surfactants have excellent compatibility with all kinds of surfactants. In addition, the nonionic surfactant is known to be not significantly affected by the physical properties of the aqueous solution of the surfactant due to the presence of pH or inorganic salts, and excellent in terms of safety to the human body.

However, since the conventional nonionic surfactant is generally in the form of ethylene oxide added, the solubility in water decreases as the temperature increases, and when the nonionic surfactant aqueous solution is heated, the solution turns cloudy after a certain temperature. Elution causes loss of function as a surfactant. In addition, ethylene oxide-based nonionic surfactants have low bubble stability and have a low temperature or a high temperature clouding point, thereby limiting various industrial applications.

On the other hand, attempts have been made to improve the cleaning power by appropriately utilizing the properties of such nonionic surfactants. In Korean Patent No. 0933761, a nonionic surfactant having high water solubility and having a low cloud point, polypropylene glycol, Disclosed is a block copolymer structure having unit-poly (ethylene oxide-propylene oxide) random copolymer unit-polypropylene glycol-poly (ethylene oxide-propylene oxide) -polypropylene glycol unit to impart improved cleaning power Although it is intended to be utilized as a surfactant of the cleaning composition, the manufacturing method is very complicated, in terms of washing power, there is a problem that the penetration power into the fiber is weak when removing the stinging of the fiber.

Accordingly, the present invention has been made to solve the above problems, as a composition for use as a non-ionic surfactant mixed in a low-foaming detergent composition, the penetration of the fibers, such as fibers to improve the cleaning power as well as improving In order to provide a composition capable of securing a good raw material appearance and chemical stability at room temperature.

It is also an object of the present invention to provide a method for preparing the composition simply by utilizing existing addition reactions.

In order to solve the above problems, the present invention provides a copolymer in which an ethylene oxide-propylene oxide is block or randomly bonded to a higher alcohol having 8 to 18 carbons, prepared under a basic catalyst.

In addition, the added mole number of the ethylene oxide is 5 to 12 moles, and the added mole number of the propylene oxide is 2 to 7 moles provide a copolymer.

In addition, the copolymer is characterized in that the basic catalyst is removed.

In addition, it provides a copolymer, characterized in that the cation content constituting the basic catalyst is 10ppm or less.

In addition, the copolymer provides a copolymer for use as a nonionic surfactant mixed in a low-foaming detergent composition.

The present invention to solve the above another problem, (a) stirring 1 mol parts of higher alcohol having 8 to 18 carbon atoms and 0.001 to 0.1 mol parts of the basic catalyst; (b) aging 5 to 12 mole parts of ethylene oxide and 2 to 7 mole parts of propylene oxide sequentially or simultaneously with the higher alcohol and then aging; And (c) removing the basic catalyst by introducing a dehumidifying member to provide a method for preparing a copolymer in which ethylene oxide-propylene oxide is block or randomly bonded to a higher alcohol.

In addition, the basic catalyst provides a production method, characterized in that potassium hydroxide (KOH) or sodium hydroxide (NaOH).

In addition, the denitration member provides a manufacturing method, characterized in that at least one selected from the group consisting of aluminum silicate, calcium silicate, magnesium silicate, magnesium aluminum silicate, calcium aluminum silicate and calcium magnesium silicate.

In addition, the step (d) provides a production method characterized in that the cation content constituting the basic catalyst is carried out to 10 ppm or less.

According to the present invention, by introducing propylene oxide into the higher alcohol ethylene oxide, it is possible to provide a composition having low foamability and improved cleaning power and appearance at room temperature.

In addition, by applying a higher alcohol to the ethylene oxide-propylene oxide copolymer can provide a composition having improved penetration into the object to be cleaned, such as fibers.

In addition, it is possible to decompose the remaining catalyst in the composition to provide a composition ensured chemical stability.

In addition, it is possible to provide a method for simply preparing the composition by utilizing an existing addition reaction.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims and their equivalents. It is to be understood that various equivalents and modifications may be substituted for those at the time of the present application.

MEANS TO SOLVE THE PROBLEM In the nonionic surfactant mixed with the low foaming detergent composition, the present inventors do not manufacture a copolymer by a complicated method according to the prior art, but add ethylene oxide-propylene oxide to higher alcohol which has a range of carbon number through an addition reaction. It was surprisingly found that the preparation of a block or randomly bonded copolymer led to the present invention that it was surprisingly possible to provide a composition with improved cleaning power compared to the copolymer according to the prior art.

Accordingly, the present invention discloses a copolymer prepared under a basic catalyst, in which ethylene oxide-propylene oxide is blocked or randomly bonded to a higher alcohol having 8 to 18 carbon atoms.

That is, as the higher alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, and the like may be used.

The higher alcohol is added to the ethylene oxide-propylene oxide to form a straight chain alkyl chain having 8 to 18 carbon atoms in the composition, to improve the penetration of the surface of the fiber, such as the performance of the performance of the activity, especially when crushed such as fibers It works very effectively for cleaning.

The higher alcohol is a nonionic surfactant and is a condition for satisfying the object of the present invention, and considering the relationship between the penetration force of the copolymer according to the present invention to the object to be cleaned, the solubility in water and cloud point, It should be 8-18.

Ethylene oxide and propylene oxide added to the higher alcohol is a hydrophilic portion of the nonionic surfactant, the number of moles added in relation to the water solubility and cloud point of the copolymer according to the present invention is important, in the present invention the ethylene oxide It is preferable that the added mole number of 5-12 mol, the added mole number of the said propylene oxide is 2-7 mol, The addition mole number of the ethylene oxide is 8-10 mol, It is more preferable that the added mole number of the propylene oxide is 4-6 mol. Do.

In the case of the added propylene oxide, by lowering the cloud point in the molecule to about 45-55 ° C., hydrogen bonds are decomposed at low temperatures in the aqueous phase to separate the oil-soluble part and the water-soluble part from each other, thereby lowering the solubility in water. The cleaning power of the contaminants will be improved.

The higher alcohol ethylene oxide-propylene oxide block copolymer in the composition according to the present invention may be represented by, for example, the following formula (1).

(R is an alkyl group having 8 to 18 carbon atoms, m is 5-12, n is 2-7)

The higher alcohol ethylene oxide-propylene oxide blocks or random copolymers according to the invention are prepared under basic catalysts in order to effectively control the addition reaction to the higher alcohol. The basic catalyst may be a catalyst containing an alkali metal or alkaline earth metal, preferably potassium hydroxide or sodium hydroxide.

The basic catalyst functions poorly in appearance by clouding the liquid surfactant product after the addition reaction.

Accordingly, the present invention discloses a copolymer from which the basic catalyst has been removed. Preferably, a copolymer having a cation (metal ion) content constituting the basic catalyst is 10 ppm or less based on the total weight of the surfactant in the liquid phase.

The removal of the basic catalyst is performed using a dehumidifying member, which will be described later. The removal of the basic catalyst to 10 ppm or less eliminates the phenomenon of blurring the appearance of the product generated when the catalyst is not removed, and at the same time with the composition for the cleaning agent added during the preparation of the cleaning agent. Mixing stability can also be secured.

The higher alcohol ethylene oxide-propylene oxide block or random copolymer according to the present invention is not limited if its use is used in the cleaning composition, but in particular, it is used as a nonionic surfactant mixed in the low-foaming cleaning composition. Suitable.

The higher alcohol ethylene oxide-propylene oxide block or random copolymer according to the present invention described above can be prepared simply by addition reaction to the raw materials under a basic catalyst.

Therefore, the present invention comprises the steps of: (a) stirring 1 mol parts of the higher alcohol having 8 to 18 carbon atoms and 0.001 to 0.1 mol parts of the basic catalyst; (b) aging 5 to 12 mole parts of ethylene oxide and 2 to 7 mole parts of propylene oxide sequentially or simultaneously with the higher alcohol and then aging; And (c) removing the basic catalyst by inputting a dehumidifying member to disclose a method for preparing a copolymer in which ethylene oxide-propylene oxide is block or randomly bonded to a higher alcohol.

As the higher alcohol, octyl alcohol, cetyl alcohol, stearyl alcohol, etc. may be used, and as the basic catalyst, a catalyst including an alkali metal or an alkaline earth metal may be used. Preferably, potassium hydroxide or sodium hydroxide is used. Can be. The basic catalyst is added together with 0.001 to 0.1 mole parts with respect to 1 mole part of the higher alcohol and sufficiently stirred. The stirring is preferably carried out until the temperature in the reactor is raised to about 110 ~ 130 ℃.

After the stirring, ethylene oxide and propylene oxide addition reaction and aging are performed. The ethylene oxide and propylene oxide are sequentially added, that is, the ethylene oxide is added to add and react the propylene oxide, followed by addition and aging. When the higher alcohol ethylene oxide-propylene oxide block copolymer can be prepared, when the addition reaction and aging by adding the ethylene oxide and propylene oxide at the same time can be prepared a higher alcohol ethylene oxide-propylene oxide random copolymer.

In this case, in the case of preparing a higher alcohol ethylene oxide-propylene oxide block copolymer, the addition reaction of ethylene oxide is preferably performed for 2 to 4 hours at a reaction temperature of 140 ~ 160 ℃, the addition reaction of propylene oxide is 125 ~ 145 It is preferable to carry out for 2 to 4 hours at the reaction temperature conditions of ℃. In addition, in the preparation of the higher alcohol ethylene oxide-propylene oxide random copolymer, the addition reaction is preferably performed for 2 to 4 hours at a reaction temperature of 125 ~ 145 ℃. The aging may be performed at room temperature for 1 to 3 hours.

The added mole number of ethylene oxide and propylene oxide added to the higher alcohol is 5 to 12 moles for the ethylene oxide, 2 to 7 moles for the propylene oxide, 8 to 10 moles for the ethylene oxide, and the propylene oxide. In the case of 4-6 mol, it is more preferable.

After the final aging, the basic catalyst is removed using a denitrification member. Specifically, 0.1 to 5% by weight, preferably 1 to 3% by weight of the denitration member is added to the total weight of the aged reactant, and the temperature is 100 to 110 ° C. at 700 to 800 torr, preferably 740 to 760 torr. The basic catalyst can be removed by deodorizing under reduced pressure for 0.5 to 2 hours to remove volatiles. Thereafter, it is filtered using a filter to obtain a final higher alcohol ethylene oxide-propylene oxide copolymer.

Examples of the denitration member include aluminum silicate, calcium silicate, magnesium silicate, magnesium aluminum silicate, calcium aluminum silicate, calcium magnesium silicate, and the like, and preferably aluminum silicate or magnesium silicate may be used.

The basic catalyst in the final higher alcohol ethylene oxide-propylene oxide copolymer is 10 ppm or less by removing the basic catalyst using the dehumidifying member, thereby eliminating the phenomenon that the appearance of the product generated when the catalyst is not removed is blurred and the cleaning agent. It is also possible to ensure the stability of mixing with the composition for the cleaning agent added during manufacture.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example  One

1 mol of lauryl alcohol and 0.01 mol of potassium hydroxide were added to the reaction vessel capable of pressure reaction and heated to 120 ° C while stirring. Thereafter, 10 mol of ethylene oxide was added to the reaction vessel, followed by addition reaction at 150 ° C. for 3 hours, and then aged at room temperature for 1 hour. 6 mol of propylene oxide was added to the reaction vessel, followed by addition reaction at 135 ° C. for 3 hours, and then at room temperature. Aged 2 hours. After completion of aging, 2% by weight of aluminum silicate was added to the denitrification member, and deodorized under reduced pressure at 750torr for 1 hour at a temperature of 105 ° C to remove volatiles, followed by filtration using a filter to obtain a final higher alcohol ethylene oxide-propylene. Oxide block copolymers were prepared.

Example  2

1 mol of lauryl alcohol and 0.01 mol of potassium hydroxide were added to the reaction vessel capable of pressure reaction and heated to 120 ° C while stirring. Thereafter, 10 mol of ethylene oxide and 6 mol of propylene oxide were added to the reaction vessel, and aged for 3 hours at room temperature after addition reaction at 135 ° C for 3 hours. After completion of aging, 2% by weight of aluminum silicate was added to the denitrification member, and deodorized under reduced pressure at 750torr for 1 hour at a temperature of 105 ° C to remove volatiles, followed by filtration using a filter to obtain a final higher alcohol ethylene oxide-propylene. Oxide block copolymers were prepared.

The appearance, cloud point and potassium ion content of the copolymer prepared according to the above example was measured and the results are shown in Table 1 below.

division Example 1 Example 2 Exterior Transparency Transparency Cloud point (℃) 50.2 51.7 Potassium Ion Content (ppm) 5 7

Claims (9)

A copolymer prepared under a basic catalyst and having an ethylene oxide-propylene oxide block or randomly bonded to a higher alcohol having 8 to 18 carbon atoms. The method of claim 1,
The added mole number of the ethylene oxide is 5 to 12 moles, and the added mole number of the propylene oxide is 2 to 7 moles. The method of claim 1,
Copolymer, characterized in that the basic catalyst is removed. The method of claim 3,
And a cation content constituting the basic catalyst is 10 ppm or less. 5. The method according to any one of claims 1 to 4,
The copolymer is characterized in that for use as a nonionic surfactant mixed in a low-foaming detergent composition. (a) stirring 1 mol parts of the higher alcohol having 8 to 18 carbon atoms and 0.001 to 0.1 mol parts of the basic catalyst;
(b) aging 5 to 12 mole parts of ethylene oxide and 2 to 7 mole parts of propylene oxide sequentially or simultaneously with the higher alcohol and then aging; And
(c) adding a dehumidifying member to remove the basic catalyst;
Ethylene oxide-propylene oxide block or randomly bonded to a higher alcohol comprising a copolymer manufacturing method. The method according to claim 6,
The basic catalyst is potassium hydroxide (KOH) or sodium hydroxide (NaOH) characterized in that the production method. The method according to claim 6,
The denitration member is a manufacturing method, characterized in that at least one selected from the group consisting of aluminum silicate, calcium silicate, magnesium silicate, magnesium aluminum silicate, calcium aluminum silicate and calcium magnesium silicate. The method according to claim 6,
The step (d) is characterized in that the cation content of the basic catalyst is carried out so that the content is 10ppm or less.