High-molecular surfactant with hydrogen peroxide stabilizing function and synthesis method of high-molecular surfactant

Abstract

The invention relates to a high-molecular surfactant with a hydrogen peroxide stabilizing function. The high-molecular surfactant has a good hydrogen peroxide stabilizing function and an excellent impurity removal capability in the field of cotton refining. The preparation method comprises the following specific synthesis steps: in the presence of a catalyst and a polymerization inhibitor, carrying out a stirring reaction on fatty alcohol-polyoxyethylene ether and alpha-hydroxy acrylic acid at the reaction temperature of 80-150 DEG C for 3-12 hours, esterifying and then polymerizing to obtain a product.

Description

Technical Field

[0001] The present invention relates to the field of surfactants, and particularly to a polymer surfactant with the function of stabilizing hydrogen peroxide and a synthesis method thereof. Background Art

[0002] Surfactants are widely used in the field of cotton fabric cleaning. Cotton fiber is a natural fiber, and the fiber contains a large amount of impurities such as waxy substances, pectin, cottonseed hulls, pigments, etc., which need to be removed before dyeing. Generally, in the impurity removal process, surfactants, hydrogen peroxide stabilizers, chelating agents, caustic soda, and hydrogen peroxide are required for scouring. Among them, the hydrogen peroxide stabilizer controls the decomposition of hydrogen peroxide to prevent the generation of holes in the fabric. Traditional surfactants generally only have the performance of removing impurities and do not have the function of stabilizing hydrogen peroxide. Hydrogen peroxide stabilizers have excellent hydrogen peroxide stabilizing functions, and the scouring process requires the use of surfactants in combination with hydrogen peroxide stabilizers. However, due to the poor compatibility between traditional surfactants and hydrogen peroxide stabilizers, they are generally added to the process formula as two separate auxiliaries for scouring.

[0003] In patent CN115215952A, fatty alcohol polyoxyethylene ether AEO9 and acrylic acid are used to prepare fatty alcohol polyoxyethylene ether acrylate for use as a polymer thickener. CN114874385A uses fatty alcohol polyoxyethylene ether AEO9, acrylic acid, and sodium styrene sulfonate to prepare an anionic-nonionic polymer surfactant. The poly-fatty alcohol polyoxyethylene ether acrylate prepared from fatty alcohol polyoxyethylene ether AEO9 and acrylic acid in CN109234046A can be preferably used in the daily chemical field and has excellent detergency, thickening, and foam stabilizing properties. The above-mentioned disclosed patents all use acrylic acid as the reaction esterification raw material. Although excellent properties have been achieved in the fields of thickeners, the preparation of anionic surfactants, and the daily chemical field, due to the absence of a hydroxyl group at the α-position of acrylic acid, none of them have the function of stabilizing hydrogen peroxide. CN106758392A uses a reactive non-ionic surfactant for a thickener for dye printing. The non-ionic is an ester obtained by esterifying fatty alcohol polyoxyethylene ether AEO9 and α-hydroxy acrylic acid, and no further polymerization is carried out, and it does not have the function of stabilizing hydrogen peroxide. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a polymer surfactant with the function of stabilizing hydrogen peroxide, and the polymer surfactant not only has better impurity removal ability in the field of cotton scouring, but also has better hydrogen peroxide stabilizing function.

[0005] The technical solution of the present invention is as follows:

[0006] A polymer surfactant with the function of stabilizing hydrogen peroxide, and its structural formula is shown as follows:

[0007]

[0008] Among them, R is C 10 -C 14 long-chain alkane, and a is a = 3 - 10.

[0009] A preparation method of a polymer surfactant with a stable hydrogen peroxide function, comprising:

[0010] (1) Add fatty alcohol polyoxyethylene ether, α-hydroxyacrylic acid, a catalyst, and an inhibitor to a reactor, replace with nitrogen multiple times, and carry out an esterification reaction by stirring at 80 - 150 °C for 3 - 12 hours. After the esterification is completed, distill off water under reduced pressure to obtain an intermediate product.

[0011] (2) Add deionized water and part of the initiator to the reactor, add the intermediate product and the remaining initiator in batches, control the polymerization temperature at 80 - 98 °C, and carry out a polymerization reaction at 80 - 98 °C for 4 - 10 hours, and neutralize the pH to 5 - 8 to obtain a polymer surfactant.

[0012] In the step (1), the molar ratio of fatty alcohol polyoxyethylene ether to α-hydroxyacrylic acid is 1 - 1.2:1, preferably 1.1 - 1.2:1.

[0013] In the step (1), the catalyst is sulfuric acid, p-toluenesulfonic acid, phosphotungstic acid, and its dosage is 0.2 - 3% of the total mass of fatty alcohol polyoxyethylene ether and α-hydroxyacrylic acid. Preferably, the catalyst is p-toluenesulfonic acid and phosphotungstic acid, and the dosage is preferably 0.5 - 2%.

[0014] In the step (1), the inhibitor is hydroquinone and p-methoxyphenol, and its dosage is 0.03 - 0.1% of the total mass of fatty alcohol polyoxyethylene ether and α-hydroxyacrylic acid, preferably 0.05 - 0.1%.

[0015] In the step (1), the reaction temperature is preferably 100 - 130 °C, and the reaction time is preferably 5 - 10 hours.

[0016] In the step (2), the initiator is sodium persulfate, potassium persulfate, ammonium persulfate. Preferably potassium persulfate and ammonium persulfate. Its dosage is 1% - 5% of the mass of the intermediate product, preferably 1% - 3%.

[0017] In the step (2), the dosage of deionized water is 40 - 50% of the total mass of the raw materials in the step (2).

[0018] In the step (2), the reaction temperature is preferably 90 - 98 °C, and the reaction time is preferably 6 - 10 hours.

[0019] In step (2), the intermediate product and the remaining initiator are added in batches, for example, in 5 - 10 batches, to control the polymerization temperature at 80 - 98°C.

[0020] The beneficial effects of the present invention are as follows: The high - molecular surfactant obtained by esterifying fatty alcohol polyoxyethylene ether with α - hydroxyacrylic acid and then polymerizing shows excellent stability to hydrogen peroxide, providing a new type of multifunctional surfactant for cotton scouring. Detailed implementation manners

[0021] The following combines examples to elaborate in detail on the synthesis process provided by the present invention.

[0022] Test method for the stability effect of hydrogen peroxide:

[0023] Prepare a working solution in a conical flask containing 2 g / L of different types of surfactants, 6 g / L of 30% hydrogen peroxide, and 2 g / L of NaOH aqueous solution. Shake and heat at 98°C for 10 min, 20 min, 30 min, and 40 min respectively.

[0024] Respectively use a pipette to transfer 10 mL of the working solution residue at different times into a 250 mL volumetric flask, add 2 mL of 3 mol / L H 2 SO 4 solution, and titrate with 0.02 mol / L potassium permanganate standard solution until the solution turns slightly red and does not fade for half a minute, which is the end point. Take the average value in parallel three times. Calculate the residual hydrogen peroxide concentration;

[0025] Hydrogen peroxide decomposition rate = 1 - C 残留 / C 初始 .

[0026] Example 1

[0027] Add 290 g of isomeric decyl alcohol polyoxyethylene ether IS1003 (M = 290), 88 g of α - hydroxyacrylic acid (M = 88), 2 g of p - toluenesulfonic acid, and 0.2 g of hydroquinone into a reactor. Replace with nitrogen three times, evacuate to 0.02 MPA, raise the temperature to 100°C, and stir and react for 5 hours. Distill off water under reduced pressure to obtain intermediate product A.

[0028] Prepare an aqueous solution of sodium persulfate (2 g of sodium persulfate dissolved in 28 g of deionized water) for standby;

[0029] Add 120 g of deionized water and 2 g of the sodium persulfate aqueous solution into a round - bottom flask, raise the temperature to 90°C, add 100 g of intermediate product A and the remaining 28 g of the sodium persulfate aqueous solution in 5 batches, control the temperature at 90 ± 2°C, react for 6 h, and neutralize with sodium hydroxide to pH = 6 to obtain product 1.

[0030] Using the same method, replace the above α-hydroxyacrylic acid with an equimolar amount of acrylic acid to obtain polyisomeric decyl alcohol ether acrylate, denoted as product 1-1.

[0031] The obtained product was compared with IS1003 for its stabilizing effect on hydrogen peroxide, and the results are as follows.

[0032]

[0033] Example 2

[0034] Add 378 g of isomeric decyl alcohol polyoxyethylene ether IS1005 (M = 378), 86 g of α-hydroxyacrylic acid (M = 88), 3 g of p-toluenesulfonic acid, and 0.3 g of p-methoxyphenol to the reactor. Replace the gas with nitrogen three times, evacuate to 0.02 MPA, heat up to 110 °C, and stir and react for 6 hours. Distill off the water under reduced pressure to obtain an intermediate product.

[0035] Prepare an aqueous solution of sodium persulfate (3 g of sodium persulfate dissolved in 42 g of deionized water) for later use;

[0036] Add 230 g of deionized water and 3 g of the aqueous solution of sodium persulfate to a round-bottom flask, heat up to 92 °C, add 210 g of the intermediate product and the remaining 42 g of the aqueous solution of sodium persulfate in 6 batches, control the temperature at 92 ± 2 °C, react for 8 h, and neutralize with sodium hydroxide to pH = 7 to obtain product 2.

[0037] The obtained product was compared with IS1005 for its stabilizing effect on hydrogen peroxide.

[0038]

[0039] Example 3

[0040] Add 554 g of isomeric decyl alcohol polyoxyethylene ether IS1009 (M = 554), 75 g of α-hydroxyacrylic acid (M = 88), 8 g of phosphotungstic acid, and 0.6 g of hydroquinone to the reactor. Replace the gas with nitrogen three times, evacuate to 0.02 MPA, heat up to 130 °C, and stir and react for 8 hours. Distill off the water under reduced pressure to obtain an intermediate product.

[0041] Prepare an aqueous solution of sodium persulfate (5 g of sodium persulfate dissolved in 70 g of deionized water) for later use;

[0042] Add 330 g of deionized water and 5 g of the aqueous solution of sodium persulfate to a round-bottom flask, heat up to 96 °C, add 320 g of the intermediate product and the remaining 70 g of the aqueous solution of sodium persulfate in 8 batches, control the temperature at 96 ± 2 °C, react for 10 h, and neutralize with sodium hydroxide to pH = 7 to obtain product 3.

[0043] The obtained product was compared with 1009 for its stabilizing effect on hydrogen peroxide.

[0044]

[0045] Example 4

[0046] 330 g of isomeric tridecyl alcohol polyoxyethylene ether IS1303 (M = 330), 85 g of α-hydroxyacrylic acid (M = 88), 3 g of p-toluenesulfonic acid, and 0.4 g of hydroquinone were added to a reactor. After purging with nitrogen three times, the pressure was evacuated to 0.02 MPA, and the temperature was raised to 115 °C. The mixture was stirred and reacted for 6 hours. Water was distilled off under reduced pressure to obtain an intermediate product.

[0047] An aqueous solution of sodium persulfate (4 g of sodium persulfate dissolved in 56 g of deionized water) was prepared for later use.

[0048] 340 g of deionized water and 4 g of the aqueous solution of sodium persulfate were added to a round-bottom flask. The temperature was raised to 94 °C, and 300 g of the intermediate product and the remaining 56 g of the aqueous solution of sodium persulfate were added in 8 batches while controlling the temperature at 94 ± 2 °C. The reaction was carried out for 7 h, and then neutralized with sodium hydroxide to pH = 6 to obtain Product 4.

[0049] The obtained product was compared with IS1303 for its stabilizing effect on hydrogen peroxide.

[0050]

[0051] Example 5

[0052] 506 g of isomeric tridecyl alcohol polyoxyethylene ether IS1307 (M = 506), 80 g of α-hydroxyacrylic acid (M = 88), 10 g of sulfuric acid, and 0.5 g of p-methoxyphenol were added to a reactor. After purging with nitrogen three times, the pressure was evacuated to 0.02 MPA, and the temperature was raised to 130 °C. The mixture was stirred and reacted for 8 hours. Water was distilled off under reduced pressure to obtain an intermediate product.

[0053] An aqueous solution of sodium persulfate (6 g of sodium persulfate dissolved in 84 g of deionized water) was prepared for later use.

[0054] 310 g of deionized water and 6 g of the aqueous solution of sodium persulfate were added to a round-bottom flask. The temperature was raised to 95 °C, and 310 g of the intermediate product and the remaining 84 g of the aqueous solution of sodium persulfate were added in 9 batches while controlling the temperature at 95 ± 2 °C. The reaction was carried out for 9 h, and then neutralized with sodium hydroxide to pH = 6 to obtain Product 5.

[0055] The obtained product was compared with IS1307 for its stabilizing effect on hydrogen peroxide.

[0056]

[0057] Example 6

[0058] 638 g of isomeric tridecyl alcohol polyoxyethylene ether IS1310 (M = 638), 82 g of α-hydroxyacrylic acid (M = 88), 14 g of phosphotungstic acid, and 0.7 g of hydroquinone were added to a reactor. After three nitrogen replacements, the pressure was evacuated to 0.02 MPA, the temperature was raised to 145 °C, and the mixture was stirred and reacted for 10 hours. Water was distilled off under reduced pressure to obtain an intermediate product.

[0059] Prepare an aqueous solution of sodium persulfate (9 g of sodium persulfate dissolved in 126 g of deionized water) for later use;

[0060] 360 g of deionized water and 9 g of the aqueous sodium persulfate solution were added to a round-bottom flask. The temperature was raised to 97 °C, and 400 g of the intermediate product and the remaining 126 g of the aqueous sodium persulfate solution were added in 9 batches. The temperature was controlled at 97 ± 2 °C, and the reaction was carried out for 10 h. Sodium hydroxide was added to neutralize to pH = 7 to obtain Product 6.

[0061]

[0062] Example 7

[0063] 580 g of AEO-9 (M = 580), 80 g of α-hydroxyacrylic acid (M = 88), 6 g of sulfuric acid, and 0.5 g of hydroquinone were added to a reactor. After three nitrogen replacements, the pressure was evacuated to 0.02 MPA, the temperature was raised to 150 °C, and the mixture was stirred and reacted for 9 hours. Water was distilled off under reduced pressure to obtain an intermediate product.

[0064] Prepare an aqueous solution of sodium persulfate (7.8 g of sodium persulfate dissolved in 109.2 g of deionized water) for later use;

[0065] 330 g of deionized water and 4 g of the aqueous sodium persulfate solution were added to a round-bottom flask. The temperature was raised to 95 °C, and 350 g of the intermediate product and the remaining 113 g of the aqueous sodium persulfate solution were added in 9 batches. The temperature was controlled at 95 ± 2 °C, and the reaction was carried out for 9 h. Sodium hydroxide was added to neutralize to pH = 7 to obtain Product 7.

[0066] The obtained product was compared with AEO-9 for its stabilizing effect on hydrogen peroxide.

[0067]

[0068]

Claims

1. A polymer surfactant having the function of stabilizing hydrogen peroxide, the structural formula of which is as follows: in, R is C 10 -C 14 Long chain alkane, a is a=3-10.

2. A method for preparing a polymer surfactant having the function of stabilizing hydrogen peroxide, comprising: (1) adding fatty alcohol polyoxyethylene ether, α-hydroxy acrylic acid, a catalyst, and a polymerization inhibitor into a reactor, replacing the atmosphere with nitrogen for multiple times, and performing an esterification reaction. After the esterification is completed, water is distilled off under reduced pressure to obtain an intermediate product; (2) Deionized water and part of the initiator are added into the reactor, and the intermediate product and the remaining initiator are added in batches for reaction and neutralization to obtain a polymer surfactant.

3. The preparation method according to claim 2, wherein In the step (1), the molar ratio of fatty alcohol polyoxyethylene ether to α-hydroxy acrylic acid is 1-1.2:

1.

4. The preparation method according to claim 2 or 3, wherein In the step (1), the catalyst is selected from sulfuric acid, p-toluenesulfonic acid, and phosphotungstic acid, and its usage is 0.2-3% of the total mass of fatty alcohol polyoxyethylene ether and α-hydroxy acrylic acid.

5. The preparation method according to claim 2 or 3, wherein: In the step (1), the inhibitor is selected from hydroquinone and p-methoxyphenol, and its usage is 0.03-0.1% of the total mass of fatty alcohol polyoxyethylene ether and α-hydroxy acrylic acid.

6. The preparation method according to claim 2, wherein: In the step (1), the reaction temperature is 80-150° C. and the reaction is stirred for 3-12 hours.

7. The preparation method according to claim 2, wherein: In the step (2), the initiator is selected from sodium persulfate, potassium persulfate, and ammonium persulfate, and its usage is 1%-5% of the mass of the intermediate product.

8. The preparation method according to claim 2, wherein: In the step (2), the polymerization reaction is carried out at 80-98° C. for 4-10 hours.

9. The preparation method according to claim 2, wherein: In the step (2), the pH is neutralized to 5-8.

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