Ultra-long-chain glucosyl nonionic surfactant and synthesis method thereof

Abstract

The invention relates to an ultra-long-chain glucosyl nonionic surfactant and a synthesis method thereof. The surfactant is synthesized in one step through selective amination reaction catalyzed by DMAP by taking plant-based fatty acid such as arachidonic acid, behenic acid or xylinic acid as a hydrophobic tail chain and glucose derivatives such as meglumine and glucamine as a hydrophilic head group. According to the method, the hydroxyl protection / deprotection step in the traditional process is innovatively avoided, and the synthesis path is remarkably simplified. Methanol, ethanol or chloroform (single or mixed solvent) is used as a reaction medium, and the product is purified by combining an industrial crystallization method, so that the method has the advantages of simple process and low cost, and is suitable for large-scale production. The raw materials of the obtained super-long-chain glucosyl nonionic surfactant are all derived from agricultural product processing products such as rapeseeds, nuts and glucose and have reproducibility and environmental compatibility, and the characteristic of easy biodegradation of the super-long-chain glucosyl nonionic surfactant conforms to the green chemical principle.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of ultra-long chain surfactants, and particularly relates to an ultra-long chain glucosyl non-ionic surfactant. Background Art

[0002] Ultra-long chain non-ionic surfactants have shown important application potential in fields such as fracturing fluid systems, fluid drag reduction control, and rheological property optimization due to their strong viscosity-increasing characteristics under low concentration conditions. Their hydrophobic tail chains are derived from agricultural by-products such as rapeseed, nuts, and peanuts, making these non-ionic surfactants significantly renewable. However, currently commercially available products mostly use petroleum-based chemical derivatives such as polyether groups and alkyl alcohols as hydrophilic head groups, significantly reducing the sustainability of the entire molecular system. This structural contradiction highlights the urgent need to develop a green surfactant system with fully renewable and environmentally friendly components.

[0003] In recent years, using glucose, the hydrolysis product of starch, as a raw material to prepare glucosyl surfactants by synthesizing glucose derivatives has become an ideal strategy to replace petroleum-based surfactants. Compared with traditional petroleum-based hydrophilic head groups, glucose derivatives not only have excellent hydrophilic properties but also have advantages such as biological renewability, high safety for humans, low toxicity, and low irritation, and thus have become one of the hotspots in the field of surfactant research. Therefore, the fully renewable, environmentally friendly, and easily biodegradable raw materials of ultra-long chain glucosyl non-ionic surfactants conform to the concepts of green chemistry and sustainable development, providing a new idea for constructing a renewable surfactant system. Summary of the Invention

[0004] The purpose of the present invention is to provide an ultra-long chain glucosyl non-ionic surfactant and its synthesis method in view of the deficiencies of the prior art, so as to obtain a green ultra-long chain non-ionic surfactant with fully renewable components.

[0005] An ultra-long chain glucosyl non-ionic surfactant provided by the present invention has the following structural formula:

[0006]

[0007] In the said structural formula, R1 in the hydrophilic head group is -CH3 or -CH2CH3;

[0008] In the said structural formula, the hydrophobic tail chain is a saturated alkyl chain, and n is 9, 10, or 11.

[0009] The synthesis method of the ultra-long chain glucosyl non-ionic surfactant provided by the present invention includes the following steps:

[0010] Step 1:

[0011] Add meglumine or N-ethylglucamine into a solvent together, and add the catalyst DMAP. Mix and activate the amino group by ultrasonic treatment at 40 - 60°C for 60 - 80 min to obtain solution A; dissolve arachidic acid, behenic acid or lignoceric acid in the solvent by refluxing at 65 - 70°C to obtain solution B.

[0012] Step 2:

[0013] Mix solution A and solution B, and carry out a reflux reaction at 55 - 70°C for 24 - 36 hours. After the reaction is completed, remove the organic solvent to obtain the crude product of the ultra-long-chain glucosyl nonionic surfactant.

[0014] Step 3:

[0015] Dissolve the obtained crude product in hot ethanol, carry out cooling crystallization at 5 - 15°C, and filter to obtain the purified ultra-long-chain glucosyl nonionic surfactant.

[0016] In the above method, further, the mass ratio of meglumine or N-ethylglucamine to the solvent in step 1 is 1:(65 - 70); the mass ratio of meglumine or N-ethylglucamine to the DMAP catalyst is 1:(0.001 - 0.015).

[0017] In the above method, further, the molar ratio of arachidic acid, behenic acid or lignoceric acid to meglumine or N-ethylglucamine in step 1 is 1:(0.9 - 0.95); the mass ratio of arachidic acid, behenic acid or lignoceric acid to its solvent is 1:(55 - 70).

[0018] In the above method, further, the solvent in step 1 is at least one of methanol, ethanol and chloroform.

[0019] In the above method, further, the ultrasonic method in step 1 is to use an ultrasonic mixer to mix at a frequency of 20 - 35 kHz and 40 - 60°C for 60 - 80 min to obtain solution A.

[0020] In the above method, further, in step 1, dissolve arachidic acid, behenic acid or lignoceric acid in the solvent, and reflux and dissolve by a magnetic stirrer at 55 - 75°C to obtain solution B.

[0021] In the above method, further, in step 2, use a magnetic stirrer mixer to mix solution A and solution B and carry out a reflux reaction at 500 - 1000 rpm and 55 - 70°C for 24 - 36 hours.

[0022] In the above method, further, the method for removing the organic solvent in step 2 is vacuum distillation.

[0023] In the above method, further, in step 3, the mass ratio of the crude product to ethanol is 1:(30 - 45); the temperature of the hot ethanol is 50 - 60°C.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. The ultra-long chain glucosyl nonionic surfactant of the present invention, whose main raw materials all come from biological renewable resources, meets environmental protection standards, and this surfactant has excellent renewability and safety, and has broad application prospects in the research and development field of new functional surfactants.

[0026] 2. The ultra-long chain glucosyl nonionic surfactant of the present invention, as a biological renewable surfactant, has the following advantages: gentle to the skin, low irritation; excellent wetting performance and solubilization effect; excellent interfacial activity in the oil-water system; strong ability to resist hard water; the hydrophilic head group is polyhydroxyglucosamine, having good water solubility and alcohol solubility, and its hydrophobic tail chain is an ultra-long carbon chain (≥C20), having strong thickening ability at low concentration and good rheological modification performance.

[0027] 3. In the method of the present invention, glucosamine and glucosamine ethylamine show selectivity during the amidation reaction with fatty acids, without the need for cumbersome protection treatment of the hydroxyl groups in the sugar molecules, and the operation process is simple, which is very suitable for large-scale industrial production. Description of the Drawings

[0028] Figure 1 1H NMR spectrum of the ultra-long chain glucosyl nonionic surfactant C 20 GMe synthesized in Example 1 of the present invention.

[0029] Figure 2 1H NMR spectrum of the ultra-long chain glucosyl nonionic surfactant C 20 GEt synthesized in Example 2 of the present invention.

[0030] Figure 3 1H NMR spectrum of the ultra-long chain glucosyl nonionic surfactant C 22 GMe synthesized in Example 3 of the present invention.

[0031] Figure 4 1H NMR spectrum of the ultra-long chain glucosyl nonionic surfactant C 22 GEt synthesized in Example 4 of the present invention.

[0032] Figure 5 1H NMR spectrum of the ultra-long chain glucosyl nonionic surfactant C 24 GMe synthesized in Example 5 of the present invention.

[0033] Figure 6 The nuclear magnetic resonance hydrogen spectrum of the ultra-long chain glucosyl nonionic surfactant C 24 GEt synthesized in Example 6 of the present invention.

[0034] Figure 7 The nuclear magnetic resonance hydrogen spectra of the ultra-long chain glucosyl nonionic surfactants C 20 GMe, C 22 GMe and C 24 The Fourier transform infrared spectra of C

[0035] Figure 8 The Fourier transform infrared spectra of the ultra-long chain glucosyl nonionic surfactants C 20 GEt, C 22 GEt and C 24 GEt synthesized in Examples 2, 4 and 6 of the present invention. Detailed implementation manners

[0036] The present invention will be further described in detail below in conjunction with examples, but the implementation manners of the present invention are only examples, and the protection scope of the present invention is not limited thereto.

[0037] Example 1

[0038] The ultra-long chain glucosyl nonionic surfactant C 20 GMe, and its structural formula is:

[0039]

[0040] Preparation method:

[0041] Step 1: Dissolve 2 g of glucosamine in 130 g of methanol, add 0.001 g of DMAP, and then mix for 60 min under the conditions of 40 °C and 20 kHz ultrasonic to obtain solution A; add 2.88 g of arachidic acid to 187 g of methanol and reflux at 65 °C for 30 min to obtain solution B.

[0042] Step 2: Mix solution A and solution B at a temperature of 60 °C. Use a magnetic stirring speed of 700 rpm for mixing, and then carry out a reflux reaction for 24 hours. After the reaction is completed, place the mixture under the conditions of 40 °C for reduced pressure distillation to obtain 4.32 g of a crude white solid.

[0043] Step 3: Add the obtained crude product to 115 g of ethanol for dissolution, then crystallize overnight at 15 °C, filter to obtain a white solid; then dry under reduced pressure at 40 °C to obtain 3.90 g of a white solid, and the yield is 86%.

[0044] C20 Fourier transform infrared characteristic peaks of GMe: 3200–3600 cm-1 (O-H stretching vibration peak), 2850–3160 cm-1 (C-H stretching vibration peak), 1622 cm-1 (amide I band), 1080–1360 cm-1 (C-N and C-O stretching vibration peaks).

[0045] 1 1H NMR (600 MHz, MeOD) δ 4.03 (dt, J = 7.2, 4.8 Hz, 1H), 3.82 (dd, J = 4.7, 1.7 Hz, 1H), 3.78 (dd, J = 11.2, 3.5 Hz, 1H), 3.71–3.68 (m, 1H), 3.66–3.63 (m, 2H), 3.14–3.12 (m, 2H), 2.68 (s, 3H), 2.18–2.16 (m, 2H), 1.59 (p, J = 7.0 Hz, 2H), 1.32–1.29 (m, 32H), 0.90 (t, J = 7.0 Hz, 3H).

[0046] Example 2

[0047] Ultra-long chain glucosyl surfactant C 20 GEt, whose structural formula is:

[0048]

[0049] Preparation method:

[0050] Step 1: Dissolve 2 g of glucosyl ethylamine in 130 g of methanol, add 0.008 g of DMAP, and then mix for 60 min under the conditions of 40 °C and 20 kHz ultrasound to obtain solution A; add 2.69 g of arachidic acid to 161 g of methanol and reflux at 65 °C for 30 min to obtain solution B.

[0051] Step 2: Mix solution A and solution B at a temperature of 60 °C. Use a magnetic stirring speed of 700 rpm for mixing, and then reflux and react for 24 hours. After the reaction is completed, place the mixture under reduced pressure distillation at 40 °C to obtain 4.15 g of a crude white solid.

[0052] Step 3: Add the obtained crude product to 146 g of ethanol for dissolution, then crystallize overnight at 15 °C, filter to obtain a white solid; then dry under reduced pressure at 40 °C to obtain 4.01 g of a white solid, with a yield of 93%.

[0053] C 20FT-IR characteristic peaks of GEt: 3200 - 3600 cm-1 (O–H stretching vibration peak), 2850–3160 cm-1 (C-H stretching vibration peak), 1630 cm-1 (amide I band), 1080–1360 cm-1 (C-N and C-O stretching vibration peaks).

[0054] 1 1H NMR (600 MHz, MeOD) δ 4.02 (dt, J = 8.5, 4.4 Hz, 1H), 3.83 (dd, J = 4.8, 1.7 Hz, 1H), 3.78 (dd, J = 11.2, 3.4 Hz, 1H), 3.71–3.68 (m, 1H), 3.66–3.64 (m, 2H), 3.16–3.11 (m, 2H), 3.10–3.01 (m, 2H), 2.18–2.16 (m, 2H), 1.63–1.57 (m, 2H), 1.31–1.29 (m, 35H), 0.90 (t, J = 7.0 Hz, 3H).

[0055] Example 3

[0056] Ultra-long chain glucosyl non-ionic surfactant C 22 GMe, and its structural formula is:

[0057]

[0058] Preparation method:

[0059] Step 1: Dissolve 2 g of glucosamine in 136 g of ethanol, add 0.011 g of DMAP, and then mix at 40 °C under 20 kHz ultrasonic conditions for 60 min to obtain solution A; add 3.14 g of behenic acid to 204 g of ethanol and reflux at 70 °C for 30 min to obtain solution B.

[0060] Step 2: Mix solution A and solution B at 70 °C. Use a magnetic stirring speed of 800 rpm for mixing, and then reflux and react for 24 hours. After the reaction is completed, place the mixture under reduced pressure distillation at 40 °C to obtain 4.37 g of crude white solid.

[0061] Step 3: Add the obtained crude product to 115 g of ethanol and dissolve it, then crystallize overnight at 15 °C, filter to obtain a white solid; then dry under reduced pressure at 40 °C to obtain 4.17 g of white solid, and the yield is 87%.

[0062] C 22Fourier transform infrared characteristic peaks of GMe: 3200–3600 cm-1 (O-H stretching vibration peak), 2850–3160 cm-1 (C-H stretching vibration peak), 1622 cm-1 (amide I band), 1080–1360 cm-1 (C-N and C-O stretching vibration peaks).

[0063] 1 1H NMR (600 MHz, MeOD) δ 4.01 (dd, J=11.7, 5.1 Hz, 1H), 3.82 (dd, J=4.7, 1.7 Hz, 1H), 3.78 (dd, J=11.1, 3.6 Hz, 1H), 3.71–3.68 (m, 1H), 3.66–3.63 (m, 2H), 3.09–3.08 (m, 2H), 2.66 (s, 3H), 2.18–2.15 (m, 2H), 1.59 (p, J=7.2 Hz, 2H), 1.31–1.29 (m, 36H), 0.90 (t, J=7.0 Hz, 3H).

[0064] Example 4

[0065] Ultra-long chain glucose-based non-ionic surfactant C 22 GEt, and its structural formula is:

[0066]

[0067] Preparation method:

[0068] Step 1: Dissolve 2 g of glucosyl ethylamine in 140 g of ethanol, add 0.011 g of DMAP, and then mix for 60 min under the conditions of 40 °C and 20 kHz ultrasonic to obtain solution A; add 2.93 g of behenic acid to 190 g of ethanol, and reflux at 70 °C for 30 min to obtain solution B.

[0069] Step 2: Mix solution A and solution B at a temperature of 70 °C. Use a magnetic stirring speed of 800 rpm for mixing, and then reflux and react for 24 hours. After the reaction is completed, place the mixture under the condition of 40 °C for reduced pressure distillation to obtain 4.35 g of a crude white solid.

[0070] Step 3: Add the obtained crude product to 115 g of ethanol for dissolution, then crystallize overnight at 15 °C, filter to obtain a white solid; then dry under reduced pressure at 40 °C to obtain 4.02 g of a white solid, and the yield is 92%.

[0071] C 22FT-IR characteristic peaks of GEt: 3200–3600 cm-1 (O-H stretching vibration peak), 2850–3160 cm-1 (C-H stretching vibration peak), 1630 cm-1 (amide I band), 1080–1360 cm-1 (C-N and C-O stretching vibration peaks).

[0072] 1 1H NMR (600 MHz, MeOD) δ 4.04–4.01 (m, 1H), 3.83–3.82 (m, 1H), 3.77 (dd, J = 10.9, 3.5 Hz, 1H), 3.70 (dd, J = 10.8, 5.6 Hz, 1H), 3.68–3.64 (m, 2H), 3.13–3.06 (m, 2H), 3.05–2.98 (m, 2H), 2.19–2.17 (m, 2H), 1.63–1.58 (m, 2H), 1.32–1.28 (m, 39H), 0.90 (t, J = 6.9 Hz, 3H).

[0073] Example 5

[0074] Ultra-long chain glucosyl nonionic surfactant C 24 GMe, and its structural formula is:

[0075]

[0076] Preparation method:

[0077] Step 1: Dissolve 2 g of glucosamine in 136 g of chloroform, add 0.015 g of DMAP, and then mix for 60 min under the conditions of 40 °C and 35 kHz ultrasound to obtain solution A; add 3.59 g of montanic acid to 249 g of ethanol and reflux at 70 °C for 30 min to obtain solution B.

[0078] Step 2: Mix solution A and solution B at a temperature of 60 °C. Mix at a magnetic stirring speed of 1000 rpm, and then reflux and react for 36 hours. After the reaction is completed, place the mixture under reduced pressure distillation at 40 °C to obtain 5.01 g of a crude white solid.

[0079] Step 3: Add the obtained crude product to 115 g of ethanol and crystallize overnight at 15 °C, then filter to obtain a white solid; then dry under reduced pressure at 40 °C to obtain 4.18 g of a white solid, and the yield is 79%.

[0080] C 24Fourier transform infrared characteristic peaks of GMe: 3200–3600 cm-1 (O-H stretching vibration peak), 2850–3160 cm-1 (C-H stretching vibration peak), 1623 cm-1 (amide I band), 1080–1360 cm-1 (C-N and C-O stretching vibration peaks).

[0081] 1 1H NMR (600 MHz, MeOD) δ 4.02 (dd, J = 10.6, 5.5 Hz, 1H), 3.81 (d, J = 2.7 Hz, 1H), 3.77 (dd, J = 10.9, 3.4 Hz, 1H), 3.70 (dd, J = 10.7, 5.6 Hz, 1H), 3.67–3.64 (m, 2H), 3.08–3.07 (m, 2H), 2.65 (s, 3H), 2.20–2.17 (m, 2H), 1.62–1.59 (m, 2H), 1.32–1.29 (m, 40H), 0.90 (t, J = 6.9 Hz, 3H).

[0082] Example 6

[0083] Ultra-long chain glucosyl nonionic surfactant C 24 GEt, whose structural formula is:

[0084]

[0085] Preparation method:

[0086] Step 1: Dissolve 2 g of glucosyl ethylamine in 140 g of chloroform, add 0.015 g of DMAP, and then mix for 60 min under the conditions of 40 °C and 35 kHz ultrasound to obtain solution A; add 3.17 g of montanic acid to 225 g of ethanol, and reflux at 70 °C for 30 min to obtain solution B.

[0087] Step 2: Mix solution A and solution B at a temperature of 60 °C. Mix at a magnetic stirring speed of 500 rpm, and then reflux and react for 36 hours. After the reaction is completed, place the mixture under reduced pressure distillation at 40 °C to obtain 5.15 g of a crude white solid.

[0088] Step 3: Add the obtained crude product to 115 g of ethanol and dissolve it, then crystallize overnight at 15 °C, filter to obtain a white solid; then dry under reduced pressure at 40 °C to obtain 4.92 g of a white solid, with a yield of 93%.

[0089] C 24FT-IR characteristic peaks of GEt: 3200–3600 cm-1 (O-H stretching vibration peak), 2850–3160 cm-1 (C-H stretching vibration peak), 1630 cm-1 (amide I band), 1080–1360 cm-1 (C-N and C-O stretching vibration peaks).

[0090] 1 1H NMR (600 MHz, MeOD) δ 4.05–4.02 (m, 1H), 3.84 (d, J = 3.0 Hz, 1H), 3.79 (dd, J = 10.9, 3.6 Hz, 1H), 3.72 (dd, J = 10.3, 5.8 Hz, 1H), 3.70–3.66 (m, 2H), 3.13–3.07 (m, 2H), 3.05–2.98 (m, 2H), 2.22–2.20 (m, 2H), 1.62 (p, J = 7.1 Hz, 2H), 1.34–1.28 (m, 43H), 0.91 (t, J = 6.9 Hz, 31H).

Claims

1. A very long chain glucose-based nonionic surfactant, characterized in that: Its structural formula is as follows: In the formula, R1 is CH3 or CH2CH3, and n is 9, 10 or 11.

2. The ultra-long-chain glucose-based nonionic surfactant according to claim 1, characterized in that: In the structural formula, the raw material of the hydrophobic tail chain is selected from one of arachidic acid, behenic acid and lignoceric acid, and the raw material of the hydrophilic head group is selected from glucose derivatives such as methylglucamine or ethylglucamine.

3. The method for synthesizing the ultra-long-chain glucose-based nonionic surfactant according to claim 1, characterized in that: The following steps are involved: Step 1: Adding meglumine or ethylglucamine together to a solvent, and adding a catalyst DMAP, mixing and activating the amine group by ultrasonication at 40-60° C. for 60-80 minutes, to obtain a solution A; dissolving arachidic acid, behenic acid or lignoceric acid in a solvent under reflux at 65-70° C., to obtain a solution B; Step 2: The solution A and the solution B are mixed, and refluxed at 55 to 70° C. for 24 to 36 hours. After the reaction is completed, the organic solvent is removed to obtain a crude product of a super-long-chain glucose-based nonionic surfactant; Step 3: The obtained crude product is dissolved in hot ethanol, cooled and crystallized at 5-15° C., and filtered to obtain the purified ultra-long-chain glucose-based nonionic surfactant.

4. The method according to claim 3, characterized in that: In step 1, the mass ratio of meglumine or ethylglucamine to the solvent is 1:(65-70); the mass ratio of meglumine or ethylglucamine to the catalyst is 1:(0.001-0.015).

5. The method according to claim 3, characterized in that: In step 1, the molar ratio of arachidic acid, behenic acid or lignoceric acid to meglumine or ethylglucamine is 1:(0.9-0.95); the mass ratio of arachidic acid, behenic acid or lignoceric acid to its solvent is 1:(55-70).

6. The method according to any one of claims 3 to 5, characterized in that: The solvent in step 1 is at least one of methanol, ethanol and chloroform.

7. The method according to any one of claims 3 to 5, characterized in that: The ultrasonic method in step 1 is to use an ultrasonic mixer to mix at a frequency of 20 to 35 kHz and 40 to 60° C. for 60 to 80 minutes to obtain solution A.

8. The method according to any one of claims 3 to 5, characterized in that: In step 1, arachidic acid, behenic acid or lignoceric acid is dissolved in a solvent, and refluxed at 55-75° C. by a magnetic stirrer to obtain a solution B.

9. The method according to any one of claims 3 to 5, characterized in that: Step 2: Solution A and solution B are refluxed at 500-1000 rpm and 55-70° C. for 24-36 hours using a magnetic stirring mixer.

10. The method according to any one of claims 3 to 5, characterized in that: In step 3, the mass ratio of the crude product to ethanol is 1:(30-45); the temperature of the hot ethanol is 50-60°C.

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