KR100482289B1 - Stabilizer composition useful for peroxide bleaching and method for stabilizing peroxide bleaching agent - Google Patents

Abstract

Disclosed is a peroxide stabilizer composition that prevents decomposition of peroxides, thereby reducing the amount of peroxide bleach used and is stable to temperature or pH changes. The stabilizer composition according to the present invention comprises 10 to 25% by weight of the copolymer of Formula 1, 5 to 35% by weight of the copolymer of Formula 2 and 40 to 85% by weight of water as a solvent.

[Formula 1]

 [Formula 2]

In Chemical Formulas 1 and 2, n is an integer of 1 to 10000.

Description

Stabilizer composition useful for peroxide bleaching and method for stabilizing peroxide bleaching agent

The present invention relates to a stabilizer composition used for peroxide bleaching and a method for stabilizing peroxide bleach , and more particularly, to prevent peroxide decomposition and to reduce the amount of peroxide bleach used, and to stabilize the stabilizer composition stable to temperature or pH changes. It is about.

Hydrogen peroxide, which is a representative peroxide, is an inorganic industrial chemical useful as an oxidizing agent, and is widely used in fields such as bleaching of fibers and pulp, sterilization solution, organic synthesis reaction, and the like, and recently, it is also used for wafer cleaning in the electronic industry. Such hydrogen peroxide tends to gradually deteriorate due to the decomposition of hydrogen peroxide during transportation, storage or use, which is catalyzed by hydrogen peroxide by impurities such as various metal ions or precipitated metal compounds contained in the aqueous hydrogen peroxide solution. Because it is decomposed. That is, a way, the heavy metal ions, such as hydrogen peroxide and iron (Fe), manganese (Mn) reaction as shown in schemes 1 and 2 the free radical (Free radical) is formed, the formed free radical is decomposed again into contact with hydrogen peroxide Induces undesirable homolysis resulting in the consumption of hydrogen peroxide.

Therefore, the presence of heavy metal ions in the bleaching process in which hydrogen peroxide is used as a bleaching agent promotes the decomposition of hydrogen peroxide, thereby exhibiting no activity, loss of its function, and the resulting free radicals attack the fibers , resulting in the weakening of the fibers bleached. Sometimes.

Various stabilizers for preventing such decomposition of hydrogen peroxide are generally used. The most common stabilizers used for bleaching with alkaline peroxides are water glass (sodium silicate), which is used to bleach mechanical pulp and waste paper to make de-inked pulp (DIP). It is also used in the repulping and bleaching processes. Water glass is effective in stabilizing alkaline peroxides against metal ions that can form precipitates such as iron. However, there is a disadvantage that water glass should be used in relatively large quantities. In addition, in the process of producing paper by further treating the pulp, when the pH is lowered by neutralizing the pulp, the water glass has a disadvantage of forming a scaling with other ions, for example calcium in the water. As other stabilizers for inhibiting the activity of metals that catalytically decompose hydrogen peroxide, inorganic compounds such as pyrophosphate and tartarate, organic compounds such as organic chelating agents and organic acids are known. Inorganic acid salts are inexpensive, but pyrophosphate is decomposed into orthophosphoric acid in a high-temperature hydrogen peroxide environment, reducing stabilization ability over time, and stannate may not only corrode aluminum containers. Since it contains heavy metals, it is not environmentally preferable, and there is a problem that evaporation residues remain after use of the bleach. Organic chelate compounds, which are organic acids, are commonly used in pretreatment processes to remove heavy metal ions and are effective, but usually cannot be used alone in alkaline peroxide bleaching processes in which heavy metals are present, either partially or wholly in the form of insoluble precipitates. Phosphate is less deterioration due to hydrogen peroxide, but alone has a disadvantage in that a large amount of stabilizing effect of hydrogen peroxide is used.

Accordingly, it is an object of the present invention to provide a stabilizer composition and a method of stabilizing peroxide bleach, which are used for peroxide bleaching , which can effectively prevent decomposition of peroxides and thereby reduce the amount of peroxide used .

Another object of the present invention is to provide a stabilizer composition and a method for stabilizing peroxide bleach , which are not only stable to changes in temperature or pH, but also have excellent dispersibility and do not cause foaming.

Still another object of the present invention is to provide a stabilizer composition used for peroxide bleaching and a method for stabilizing peroxide bleach, which can minimize scale generation.

It is another object of the present invention to provide a stabilizer composition and a method for stabilizing peroxide bleach that are used for peroxide bleaching , which are environmentally preferable and do not leave evaporation residue after use, since they do not contain a phosphorus (P) component. .

In order to achieve the above object, the present invention provides a stabilizer composition for a peroxide bleach comprising a copolymer of the general formula (1): polyamine polycarboxylic acid of the general formula (2) in a ratio of 1: 0.5 to 1: 1.5 by weight.

[Formula 1] In Formula 1 n is an integer of 1 to 10000.

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 [Formula 2]

In Formula 2, n is an integer of 1 to 10000.

Here, the stabilizer composition preferably comprises 10 to 25% by weight of the copolymer of Formula 1, 5 to 35% by weight of the copolymer of Formula 2 and 40 to 85% by weight of water as a solvent.

In addition, the present invention is a peroxide in a ratio of 1: 0.5 to 1: 1.5 by weight of a copolymer of 1-allyloxy-2-hydroxypropylsulfonate and acrylic acid and a polymer formed by a condensation reaction of polyamine and β-chloroacetic acid. Provided is a method for stabilizing a peroxide bleach, which is added to a bleach.

Hereinafter, the present invention will be described in more detail.

The stabilizer composition for peroxide bleach according to the present invention is a copolymer of 1-allyloxy-2-hydroxypropyl sulphonate (AHPS) and acrylic acid as a copolymer having the structure of formula 1 Include.

In Formula 1 n is an integer of 1 to 10000. Since the polymerization degree n of the copolymer of Formula 1 does not have a special effect on the stability of the peroxide, it can be appropriately adjusted according to the convenience of manufacture, management, and handling, and when n exceeds 10,000 in terms of manufacturing and handling It is disadvantageous. The copolymer of Chemical Formula 1 may be synthesized by a conventional radical polymerization method. For example, a certain amount of water and a water-soluble peroxide initiator are placed in a reactor, the reactor temperature is maintained at 80 to 100 ° C., 1-allyloxy-2-hydroxypropylsulfonate and an acrylic acid monomer, initiator, and If necessary, a chain transfer agent such as a water-soluble thio compound is added dropwise at a constant rate for 4 to 6 hours. Next, while maintaining the temperature of the reactor at 80 to 100 ℃ can proceed the reaction further for 2 to 4 hours so that the monomer does not remain to obtain a copolymer of formula (1).

In addition, the stabilizer composition according to the present invention comprises a polyamine polycarboxylic acid of the formula (2) formed by condensation of polyamine and β-chloroacetic acid.

In Formula 2, n is an integer of 1 to 10000. Polymerization degree n of the polyamine polycarboxylic acid of Chemical Formula 2 also does not have a special effect on the stability of the peroxide, can be appropriately adjusted according to the ease of manufacture, management, handling, if n is greater than 10000 It is disadvantageous in terms of handling. For example, the polyamine polycarboxylic acid of Chemical Formula 2 may be reacted with hydrocyanic acid or sodium cyanide and formaldehyde, or the polyamine, as is commonly known . It can be prepared by dropwise reaction of 50% β-haloacetic acid, preferably β-chloroacetic acid, in a nitrogen purging state in a reactor containing a polyamine capable of forming a polymer . At this time, it is preferable to add dropwise 40% NaOH in accordance with the dropping rate of β-chloroacetic acid, and proceed the whole process under a pressurization condition of 1-2Kgf / cm ² . Here, the second method does not use a highly toxic hydrocyanic acid or a salt thereof, which is advantageous for reacting polyamines having a high degree of polymerization.

The copolymer of Chemical Formula 1 refers to a filtrate dehydrated in a white paper (white water: papermaking process), a metal ion compound present in a large amount in pulp fibers, fillers, calcium and magnesium ions, water containing various chemicals (Scalant: scale) In addition to delaying the precipitation or precipitation of the forming agent (including the hardness component), the saturated pH region of each metal ion is increased to prevent the formation of hydroxide form in the bleaching process, thereby preventing the decomposition of hydrogen peroxide. In addition, the polymer electrolyte of Chemical Formula 1 is adsorbed at the active point of the crystal nucleus and crystals, thereby preventing the formation of crystal nuclei or critical nuclei and growth of crystals, and dispersing the crystals.

The polymers of Chemical Formulas 1 and 2 strongly bind to metal ions such as Fe ³⁺ and Mn ²⁺ , thereby preventing radicals from being formed by blocking metal ions from reacting with hydrogen peroxide. In particular, the compound of Formula 1 is strongly bound with Fe ^3+, and the compound of Formula 2 is expected to be strongly bound with Mn ²⁺ . In addition, when the silicate (Silicate) is used to some extent for the stability and alkali buffer of hydrogen peroxide, the polymers of Formulas 1 and 2 prevent the condensation reaction and scaling of the silicate to further improve the stability of hydrogen peroxide.

The stabilizer composition for a peroxide bleach according to the present invention comprises a copolymer of Formula 1: the polymer of Formula 2 in a weight ratio of 1: 0.5 to 1: 1.5, preferably 1: 0.8 to 1: 1.2. In the case where the weight ratio of the polymer of Formula 2 is less than 0.5, the stability effect on Mn ²⁺ is lowered, and when it exceeds 1.5, the stability effect on Fe ³⁺ is lowered so that the overall stability effect of the peroxide is lowered. have.

The stabilizer composition for hydrogen peroxide bleach according to the present invention may include water as a solvent for dissolving the polymers of Formulas 1 and 2 for convenience of manufacture, storage, transport and use. In this case, the total stabilizer composition is 10 to 25% by weight, preferably 15 to 20% by weight of the copolymer of Formula 1, 5 to 35% by weight, preferably 10 to 20% by weight of the copolymer of Formula 2 It is preferable to include 40 to 85% by weight of water as a. Here, when the content of the solvent is less than 40% by weight, the viscosity of the stabilizer composition is too high, the handleability is lowered, and when the content of the solvent exceeds 85% by weight, the weight and volume of the composition are unnecessarily increased to store and handle Is disadvantageous.

The stabilizer composition according to the present invention is used in addition to the peroxide aqueous solution bleaching agent, each component of the stabilizer may be mixed and added to the bleaching agent, or may be separately added to the bleaching agent. In this case, the amount of stabilizer is appropriately added to 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on the solid content (polymer and copolymer) of the stabilizer composition according to the present invention, based on 100 parts by weight of hydrogen peroxide. When the amount of the solid content of the composition according to the present invention is less than 0.5 parts by weight, the stability effect of hydrogen peroxide cannot be sufficiently obtained, and even more than 20 parts by weight, no further stability effect can be obtained, and only economically disadvantageous. The stabilizer composition for hydrogen peroxide bleach according to the present invention is not only used as a stabilizer for stabilizing hydrogen peroxide, but may also be used as a precipitation regulator and does not contain phosphate, which is particularly useful for the bleaching process of pulp or paper.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by these examples.

Example 1

Synthesis of Copolymer of 1-allyloxy-2-hydroxypropylsulfonate and acrylic acid

An appropriate amount of water and a water-soluble peroxide initiator were added to a SUS316 material reactor having a volume of 8 m 3, and the temperature of the reactor was heated to 90 ° C. Next, 200 Kg of 1-allyloxy-2-hydroxypropyl sulfonate monomer, 72 Kg of acrylic acid monomer, and 1 mol% of the acrylic acid monomer were added dropwise at a constant rate for 5 hours at a constant rate. Finally, while maintaining the temperature of the reactor at 90 ℃ further reaction was carried out for 3 hours so that no monomer remained to obtain the title copolymer.

Synthesis of Condensation Reaction Polymer of Polyamine and β-Chloroacetic Acid

200 Kg of polyamine (n = about 50) was added to an 8 m 3 volumetric SUS316 reactor, and 1080 Kg of 50% β-chloroacetic acid was added dropwise under nitrogen purge to obtain the title polymer. At this time, the dropwise addition of 40% NaOH in accordance with the dropping rate of β-chloroacetic acid was added dropwise, the entire process was carried out under a pressure condition of 1-2Kgf / ㎠.

Preparation of Stabilizer Composition

A stabilizer composition was prepared by mixing 100 Kg of the obtained 1-allyloxy-2-hydroxypropylsulfonate and acrylic acid, 100 Kg of a polyamine and a condensation reaction polymer of β-chloroacetic acid, and 300 Kg of water in a reactor having a volume of 8 m 3. .

[Stability Test]

11.4% by weight of 1-allyloxy-2-hydroxypropylsulfonate and acrylic acid copolymer, 11.4% by weight of polyamine and β-chloroacetic acid condensation reaction polymer (22.8% by total solid component, the remaining amount after evaporation at 110 ° C) The stability of the hydrogen peroxide bleach on the stabilizer composition, including the measurement), was measured as follows. The phosphorus (P) content of the stabilizer composition used was 0%.

A solution was prepared containing different amounts of Fe, Mn and Ca in the form of sulfate salts, containing 4 0 mg / l (amount of solids) stabilizer, maintaining the pH of the solution at 10 with NaOH, The temperature of was adjusted to 50 ° C. Hydrogen peroxide was added while stirring the solution, while adjusting the pH, the concentration of hydrogen peroxide was measured with time using standard iodometry and the results are shown in FIGS. 1 and 2. 1 is a graph measuring the concentration of hydrogen peroxide in the bleach with or without Mn, Fe and the stabilizer of the present invention, Figure 2 is a hydrogen peroxide in bleach with or without Mn, Fe, Ca and the stabilizer of the present invention This is a graph of concentration measured over time. 1 and 2, when the stabilizer according to the present invention is added, it can be seen that the decrease in the concentration of hydrogen peroxide is significantly reduced regardless of the amount of Fe, Mn and Ca ions.

 [Bleaching test]

Industrial TMP pulp samples were bleached using hydrogen peroxide bleach, including the stabilizer used in the stability test. The initial brightness of the pulp was 60.72% ISO. Bleaching was carried out at a temperature of 70 ° C., initial pH of 10.4, hydrogen peroxide (H ₂ O ₂ ) content of 25 kg / Adt, sodium hydroxide (NaOH) content of 25 kg / Adt for 90 minutes, depending on the amount of stabilizer. The residual amount of hydrogen peroxide and the whiteness of the pulp were measured, and a control test was performed on water glass (waterglass, SiO₂: Na ₂ O = 2.5: 1) , which is a common stabilizer, to compare the results of the bleaching test . The results are shown in Table 1. It was. From Table 1 , it can be seen that the stabilizer according to the invention improves the residual amount and whiteness of hydrogen peroxide even when using a much smaller amount than conventional water glass. Type and content of stabilizer (kg / ADt) Residual Hydrogen Peroxide (kg / ADt) Whiteness (%) Stabilizer 0 of the Inventive Example 3.6 67.4 Stabilizer 0.5 of the Inventive Example 6.6 69.6 Stabilizer 1 of the Inventive Example 7.9 69.6 Stabilizer 2 of the Inventive Example 9.0 70.3 Stabilizer 4 of the Inventive Example 9.9 70.6 Water glass 0 3.6 67.4 Water glass 5 5.3 69.2 Water glass 10 7.2 70.0 Water glass 15 9.7 70.7 Water glass 20 9.4 70.9

As described above, the stabilizer composition for hydrogen peroxide bleach according to the present invention can effectively prevent the decomposition of hydrogen peroxide to reduce the amount of hydrogen peroxide used, and is stable to changes in temperature or pH, has excellent dispersion, and causes foaming. I never do that. In addition, the composition according to the present invention does not contain a heavy metal component or phosphorus (P), it is not only environmentally preferable, but also can prevent the remaining of evaporation after use.

1 is a graph measuring the concentration of hydrogen peroxide in the bleach according to the content of Mn, Fe and the stabilizer according to an embodiment of the present invention over time.

Figure 2 is a graph measuring the concentration of hydrogen peroxide in the bleach according to the content of Mn, Fe, Ca and the stabilizer according to an embodiment of the present invention over time.

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Claims (5)

Copolymer of the general formula (1): Stabilizer composition for a peroxide bleach comprising a polymer of the general formula (2) in a ratio of 1: 0.5 to 1: 1.5 by weight. [Formula 1] In Formula 1 n is an integer of 1 to 10000.  [Formula 2] In Formula 2, n is an integer of 1 to 10000. According to claim 1, wherein the stabilizer composition is 10 to 25% by weight of the copolymer of Formula 1, 5 to 35% by weight of the copolymer of Formula 2 and 40 to 85% by weight of water as a solvent for the peroxide bleach Stabilizer composition. The stabilizer composition for peroxide bleach according to claim 1, wherein the peroxide is hydrogen peroxide. The stabilizer composition for peroxide bleach according to claim 1, wherein the stabilizer composition is used in a bleaching process of pulp or paper. A copolymer of 1-allyloxy-2-hydroxypropylsulfonate and acrylic acid and a polymer formed by condensation of polyamine and β-haloacetic acid were added to the peroxide bleach in a ratio of 1: 0.5 to 1: 1.5 by weight. Method for stabilizing peroxide bleach, characterized in that.