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

Abstract

The invention discloses an ultra-long chain glucosamide nonionic surfactant and a synthesis method thereof. A hydrophobic tail chain of the surfactant is from plant-based fatty acid such as oleic acid, erucic acid or nervonic acid, and a hydrophilic head group is from glucose derivatives such as meglumine and glucamine. According to the method, oleic acid, erucic acid and nervonic acid in rapeseed byproducts are used as hydrophobic tail chain raw materials, glucose derivatives meglumine and glucamine are used as hydrophilic head group raw materials, methanol, ethanol, ethylene glycol or propylene glycol (a single solvent or a binary mixed solvent) is used as a solvent, DMAP or NaF is used as a catalyst, and the bio-based surfactant is obtained. The super-long-chain glucosamide nonionic surfactant is prepared through selective amination reaction, tedious protection on hydroxyl in glucosamine molecules is not needed, the reaction temperature is close to the room temperature, operation is easy and convenient, only a simple industrial crystallization method is needed in the purification process, and the method is suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the field of surfactant preparation, and specifically relates to an ultra-long-chain glucose amide nonionic surfactant. Background Art

[0002] Surfactants are known as "industrial MSG" and are widely used in food processing, daily chemicals, biopharmaceuticals and other fields. However, with the gradual depletion of petroleum resources, the production of traditional petroleum-derived surfactants has been gradually restricted, especially petroleum-based surfactants such as linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS) and alkylphenol polyoxyethylene ether (APE), which have poor environmental degradation and are potentially toxic to aquatic organisms. Therefore, it is particularly urgent to develop a renewable, environmentally friendly and easily degradable green surfactant.

[0003] The synthesis of glucose-based surfactants by using glucose obtained by starch hydrolysis has become a preferred alternative to petroleum-based surfactants. Compared with traditional petroleum-based surfactants, glucose-based surfactants not only have excellent biodegradability, but are also safe for the human body, with low toxicity and irritation, so they have become a new focus of surfactant research. In particular, ultra-long chain (≥C18) glucose-based nonionic surfactants have attracted much attention due to their extremely long hydrophobic tail chains, extremely low critical micelle concentration (CMC value), and significant viscoelasticity, gelation, shear thinning properties, etc. The hydrophobic tail chains of this type of surfactant cannot be obtained from petroleum cracking products, but can only be obtained from by-products of natural vegetable oils (such as oleic acid, erucic acid and nervonic acid in vegetable oils such as rapeseed and peanut). Therefore, the key raw materials of ultra-long chain glucose-based nonionic surfactants are not only renewable, but also environmentally friendly and easily biodegradable, meeting the requirements of green chemistry and sustainable development. Summary of the invention

[0004] The purpose of the present invention is to provide a super-long-chain glucose amide nonionic surfactant and a synthesis method thereof in view of the deficiencies in the prior art, so as to obtain an environmentally friendly and easily degradable green surfactant.

[0005] The present invention provides a super long chain glucose amide nonionic surfactant, the structure of which is shown in the following formula:

[0006]

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

[0008] In the structural formula, the hydrophobic tail chain is characterized by containing an unsaturated bond, and n is 1, 5 or 7.

[0009] The preparation method of the ultra-long chain glucose amide nonionic surfactant provided by the present invention comprises the following steps:

[0010] Step 1

[0011] Add meglumine or ethylglucamine to a solvent, and add a catalyst DMAP or NaF, mix and activate the amine group by high shear stirring at 10-30°C for 20-40 minutes to obtain solution A; dissolve oleic acid, erucic acid or nervonic acid in a solvent to obtain solution B.

[0012] Step 2

[0013] The solution A and the solution B are mixed by high shear stirring, and stirred at 10 to 30° C. for 8 to 24 hours. After the reaction is completed, the organic solvent is removed to obtain a crude product of a super-long-chain glucose amide nonionic surfactant.

[0014] Step 3

[0015] The obtained crude product is dissolved in dichloromethane, and acetone is slowly added dropwise at 15-45° C. for crystallization to obtain a purified ultra-long-chain glucose amide nonionic surfactant.

[0016] In the above method, further, in step 1, the mass ratio of meglumine or ethylglucamine to its solvent is 1:(50-60); the mass ratio of meglumine or ethylglucamine to the catalyst is 1:(0.002-0.003).

[0017] In the above method, further, the molar ratio of oleic acid, erucic acid or nervonic acid to meglumine or ethylglucamine in step 1 is 1:(0.8-0.95); the mass ratio of oleic acid, erucic acid or nervonic acid to its solvent is 1:(20-30).

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

[0019] In the above method, further, the high shear method in step 1 is to use a high shear mixer to mix at 8000-12000 rpm and 25° C. for 30 minutes to obtain solution A.

[0020] In the above method, further, in step 2, oleic acid, erucic acid or nervonic acid is dissolved in a solvent, and ultrasonic mixing is performed by an ultrasonic mixer to obtain solution B.

[0021] In the above method, further, in step 2, solution A and solution B are mixed and sheared using a high shear mixer at 25° C. and 8000-12000 rpm until they are fully mixed and uniform.

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

[0023] In the above method, further, the mass ratio of the crude product to dichloromethane in step 3 is 1:(45-55); the mass ratio of the dripped acetone to dichloromethane is 1:(0.5-0.8).

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

[0025] 1. The ultra-long-chain glucosamide nonionic surfactant of the present invention has abundant raw material sources, low price, meets environmental protection requirements, has good biodegradability and safety, and is suitable for the development of new functional surfactants.

[0026] 2. The ultra-long-chain glucose amide nonionic surfactant of the present invention as an environmentally friendly surfactant has the following advantages:

[0027] Gentle on the skin, less irritating;

[0028] Excellent wetting properties and solubilization effect;

[0029] It has good interfacial activity in oil-water system;

[0030] Shows strong resistance to hard water;

[0031] The hydrophobic tail chain is an ultra-long carbon chain (≥C18) containing an unsaturated bond, which has good rheological modification properties and better low-temperature solubility than ultra-long saturated carbon chain surfactants.

[0032] 3. In the method of the present invention, the amidation reaction of meglumine and ethylglucamine with fatty acids is a selective reaction, and there is no need to perform complicated protection treatment on the hydroxyl groups in the sugar molecules. The operation is simple and suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 1 of the present invention 18 H NMR spectrum of GMe.

[0034] Figure 2 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 2 of the present invention 18 H NMR spectrum of GEt.

[0035] Figure 3 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 3 of the present invention 22 H NMR spectrum of GMe.

[0036] Figure 4The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 4 of the present invention 22 H NMR spectrum of GEt.

[0037] Figure 5 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 5 of the present invention 24 H NMR spectrum of GMe.

[0038] Figure 6 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 6 of the present invention 24 H NMR spectrum of GEt.

[0039] Figure 7 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 1 of the present invention 18 High-resolution mass spectrometry of GMe.

[0040] Figure 8 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 2 of the present invention 18 High-resolution mass spectrometry of GEt.

[0041] Fig. 9 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 3 of the present invention 22 High-resolution mass spectrometry of GMe.

[0042] Fig.10 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 4 of the present invention 22 High-resolution mass spectrometry of GEt.

[0043] Fig.11 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 5 of the present invention 24 High-resolution mass spectrometry of GMe.

[0044] Fig.12 The ultra-long-chain glucose amide nonionic surfactant UC synthesized in Example 6 of the present invention 24 High-resolution mass spectrometry of GEt. DETAILED DESCRIPTION

[0045] The present invention is further described in detail below in conjunction with embodiments, but the embodiments of the present invention are only examples and the protection scope of the present invention is not limited thereto.

[0046] Example 1

[0047] Ultra-long chain glucose amide nonionic surfactant UC 18 GMe, its structural formula is:

[0048]

[0049] Preparation method:

[0050] Step 1: Dissolve 1 g of meglumine in 50 g of methanol, add 0.002 g of DMAP, and then mix at 25° C. and a high shear rate of 8000 rpm for 30 min to obtain solution A; dissolve 1.81 g of oleic acid in 36.2 g of methanol, and then ultrasonicate for 30 min to obtain solution B.

[0051] Step 2: Solution A and solution B were mixed at a temperature of 25°C. The mixture was mixed at a high shear rate of 10,000 rpm for 30 minutes. After mixing, the mixture was placed under a magnetic stirring condition of 200 rpm, and the reaction temperature was lowered to 10°C for 12 hours. After the reaction was completed, the mixture was placed under a reduced pressure distillation condition of 40°C to obtain 2.30 g of a yellow paste crude product.

[0052] Step 3: The obtained crude product was dissolved in 102.5 g of dichloromethane, and then 205 g of acetone was slowly added dropwise at 15°C to obtain a white solid; then the mixture was dried under reduced pressure at 35°C to obtain 2.05 g of a white solid with a yield of 87%.

[0053] 1 H NMR (400MHz, CDCl3): δ5.37–5.28(m,2H),4.11(br.,1H),3.80–3.65(m,5H),3.10(br.,2H),2.65( s,1H),2.13(br.,2H),2.00–1.99(m,4H),1.52(br.,2H),1.26(br.,20H),0.87(t,J=6.6Hz,3H).C 25 H 49 HRMS (m / z) results of NO6: [M+H] + , theoretical value, 460.3633; experimental value: 460.3633.

[0054] Example 2

[0055] Ultra-long chain glucose amide nonionic surfactant UC 18 GEt, its structural formula is:

[0056]

[0057] Preparation method:

[0058] Step 1: 1 g of ethylglucamine was dissolved in 60 g of ethanol, 0.003 g of DMAP was added, and then mixed at 25° C. and a high shear rate of 8000 rpm for 30 min to obtain solution A; 1.50 g of oleic acid was dissolved in 45 g of ethanol, and then ultrasonically treated for 30 min to obtain solution B.

[0059] Step 2: Solution A and solution B were mixed at a temperature of 25°C. The mixing was performed at a high shear rate of 10,000 rpm for 30 minutes. After mixing, the mixture was placed under a magnetic stirring condition of 200 rpm, and the reaction temperature was lowered to 20°C for 12 hours. After the reaction was completed, the mixture was placed under a reduced pressure distillation condition at 40°C to obtain 2.18 g of a yellow paste crude product.

[0060] Step 3: The obtained crude product was dissolved in 102 g of dichloromethane, and then 204 g of acetone was slowly added dropwise at 15°C to obtain a white solid; then the mixture was dried under reduced pressure at 45°C to obtain 2.04 g of a white solid with a yield of 90%.

[0061] 1 H NMR (400MHz, CDCl3): δ5.37–5.28(m,2H),4.12(br.,1H),3.81–3.66(m,5H),3.10(br.,2H),3.00(br., 2H),2.13(t,J=7.0Hz,2H),2.00–1.97(m,4H),1.52(br.,2H),1.26(br.,20H),0.87(t,J=6.6Hz,2H).C 26 H 51 HRMS (m / z) results of NO6: [M+H] + , theoretical value, 474.3789; experimental value: 474.3789.

[0062] Example 3

[0063] Ultra-long chain glucose amide nonionic surfactant UC 22 GMe, its structural formula is:

[0064]

[0065] Preparation method:

[0066] Step 1: Dissolve 1 g of meglumine in 50 g of methanol, add 0.0025 g of DMAP, and then mix at 25° C. and a high shear rate of 8000 rpm for 30 min to obtain solution A; dissolve 1.83 g of erucic acid in 40 g of methanol, and then ultrasonicate for 30 min to obtain solution B.

[0067] Step 2: Solution A and solution B were mixed at a temperature of 25°C. The mixing was performed at a high shear rate of 10,000 rpm for 30 minutes. After mixing, the mixture was placed under a magnetic stirring condition of 200 rpm, and the reaction temperature was lowered to 25°C for 12 hours. After the reaction was completed, the mixture was placed under a reduced pressure distillation condition at 40°C to obtain 2.65 g of a yellow paste crude product.

[0068] Step 3: The obtained crude product was dissolved in 123 g of dichloromethane, and then 246 g of acetone was slowly added dropwise at 25°C to obtain a light yellow solid; then it was dried under reduced pressure at 45°C to obtain 2.46 g of a light yellow solid with a yield of 93%.

[0069] 1 H NMR(400MHz, CDCl3): δ,5.38–5.30(m,2H),4.11(br.,1H),3.80–3.65(m,5H),3.10(br.,2H),2.65 (s,3H),2.14(br.,2H),2.01–1.98(m,4H),1.52(br.,2H),1.25(br.,20H),0.87(t,J=6.6Hz,3H).C 29 H 57 HRMS (m / z) results of NO6: [M+H] + , theoretical value, 516.4259; experimental value: 516.4259.

[0070] Example 4

[0071] Ultra-long-chain glucose-based surfactant UC 22 GEt, its structural formula is:

[0072]

[0073] Preparation method:

[0074] Step 1: Dissolve 1 g of ethylglucamine in 55 g of ethylene glycol, add 0.028 g of DMAP, and then mix at 25°C and a high shear rate of 8000 rpm for 30 min to obtain solution A; dissolve 1.80 g of erucic acid in 50 g of ethylene glycol, and then ultrasonicate for 30 min to obtain solution B.

[0075] Step 2: Solution A and solution B were mixed at a temperature of 25°C. The mixing was performed at a high shear rate of 12,000 rpm for 30 minutes. After mixing, the mixture was placed under a magnetic stirring condition of 200 rpm, and the reaction temperature was lowered to 20°C for 12 hours. After the reaction was completed, the mixture was placed under a reduced pressure distillation condition of 80°C to obtain 2.41 g of a yellow paste crude product.

[0076] Step 3: The obtained crude product was dissolved in 107.5 g of dichloromethane, and then 134.38 g of acetone was slowly added dropwise at 25°C to obtain a light yellow white solid; then it was dried under reduced pressure at 45°C to obtain 2.15 g of a light yellow solid with a yield of 85%.

[0077] 1 H NMR(400MHz, CDCl3): δ,5.38–5.33(m,2H),4.15(br.,1H),3.85–3.69(m,5H),3.13(br.,2H),3.03(br.,2H) ),2.18(br.,2H),2.03(dd,J=11.8,6.4Hz,2H),1.55(br.,2H),1.27–1.24(m,31H),0.90(t,J=6.8Hz,3H).C 31 H 61 HRMS (m / z) results of NO6: [M+H] + , theoretical value, 531.4493; experimental value, 531.4493.

[0078] Example 5

[0079] Ultra-long chain glucose amide nonionic surfactant UC 24 GMe, its structural formula is:

[0080]

[0081] Preparation method:

[0082] Step 1: Dissolve 1 g of meglumine in 50 g of propylene glycol, add 0.0028 g of DMAP, and then mix at 25°C and a high shear rate of 8000 rpm for 30 min to obtain solution A; dissolve 1.98 g of neuraminic acid in 57 g of methanol, and then ultrasonicate for 30 min to obtain solution B.

[0083] Step 2: Solution A and solution B were mixed at a temperature of 25°C. The mixing was performed at a high shear rate of 12,000 rpm for 30 minutes. After mixing, the mixture was placed under a magnetic stirring condition of 200 rpm, and the reaction temperature was lowered to 25°C for 12 hours. After the reaction was completed, the mixture was placed under a reduced pressure distillation condition at 40°C to obtain 2.70 g of a yellow paste crude product.

[0084] Step 3: The obtained crude product was dissolved in 130 g of dichloromethane, and then 260 g of acetone was slowly added dropwise at 45°C to obtain a white solid; then the mixture was dried under reduced pressure at 45°C to obtain 2.59 g of a crude white solid product with a yield of 93%.

[0085] 1 H NMR(400MHz, CDCl3): δ,5.38–5.30(m,2H),4.12(br.,1H),3.81–3.66(m,5H),3.10(br.,2H),2.65(s,3H) ,2.13(br.,2H),2.01(dd,J=11.8,6.4Hz,4H),1.52(br.,2H),1.26–1.25(m,32H),0.87(t,J=6.8Hz,3H).C 31 H 61 HRMS (m / z) of NO6: [M+H] + , theoretical value, 544.4572; experimental value: 544.4572.

[0086] Example 6

[0087] Ultra-long chain glucose amide nonionic surfactant UC 24 GEt, its structural formula is:

[0088]

[0089] Preparation method:

[0090] Step 1: Dissolve 1 g of ethylglucamine in 55 g of ethanol, add 0.025 g of DMAP, and then mix for 30 min at 25°C and a high shear rate of 8000 rpm to obtain solution A; dissolve 1.84 g of neuraminic acid in 52 g of ethylene glycol, and then ultrasonically treat for 30 min to obtain solution B.

[0091] Step 2: Solution A and solution B were mixed at a temperature of 25°C. The mixing was performed at a high shear rate of 12,000 rpm for 30 minutes. After mixing, the mixture was placed under a magnetic stirring condition of 200 rpm, and the reaction temperature was lowered to 20°C for 12 hours. After the reaction was completed, the mixture was placed under a reduced pressure distillation condition at 40°C to obtain 2.51 g of a yellow paste crude product.

[0092] Step 3: The obtained crude product was dissolved in 123 g of dichloromethane, and then 246 g of acetone was slowly added dropwise at 45°C to obtain a white solid; then the mixture was dried under reduced pressure at 45°C to obtain 2.45 g of a white solid with a yield of 92%.

[0093] 1 H NMR(400MHz, CDCl3): δ,5.38–5.30(m,2H),4.13(br.,1H),3.82–3.67(m,5H),3.10(br.,2H),3.01(br.,2H) ),2.13(br.,2H),2.01(dd,J=11.8,6.4Hz,2H),1.52(br.,2H),1.26–1.24(m,35H),0.87(t,J=6.8Hz,3H).C 31 H 61 HRMS (m / z) of NO6: [M+H] + , theoretical value, 558.4728; experimental value, 558.4728.

Claims

1. A super long chain glucose amide nonionic surfactant, characterized in that, Its structural formula is as follows: In the formula, R1 is CH3 or CH2CH3, and n is 1, 5 or 7.

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

3. The method for synthesizing the ultra-long chain glucose amide nonionic surfactant according to claim 1, characterized in that: The following steps are included: Step 1: Adding meglumine or ethylglucamine to a solvent, and adding a catalyst DMAP or NaF, mixing and activating the amine group by high shear stirring at 10 to 30° C. for 20 to 40 minutes, to obtain a solution A; dissolving oleic acid, erucic acid or nervonic acid in a solvent, to obtain a solution B; Step 2: The solution A and the solution B are mixed by high shear stirring, and the mixture is stirred and reacted at 10 to 30° C. for 8 to 24 hours. After the reaction is completed, the organic solvent is removed to obtain a crude product of a super-long-chain glucose amide nonionic surfactant; Step 3: The obtained crude product is dissolved in dichloromethane, and acetone is slowly added dropwise at 15-45° C. for crystallization to obtain a purified ultra-long-chain glucose amide 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:(50-60); the mass ratio of meglumine or ethylglucamine to the catalyst is 1:(0.002-0.003).

5. The method according to claim 3, characterized in that: The molar ratio of oleic acid, erucic acid or nervonic acid to meglumine or ethylglucamine in step 1 is 1:(0.8-0.95); the mass ratio of oleic acid, erucic acid or nervonic acid to its solvent is 1:(20-30).

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

7. The method according to any one of claims 3 to 5, characterized in that: The high shear method in step 1 is to use a high shear mixer to mix at 8000-12000 rpm and 25° C. for 30 minutes to obtain solution A.

8. The method according to any one of claims 3 to 5, characterized in that: In step 2, oleic acid, erucic acid or nervonic acid is dissolved in a solvent, and solution B is obtained by ultrasonic mixing using an ultrasonic mixer.

9. The method according to any one of claims 3 to 5, characterized in that: Step 2: Mix solution A and solution B using a high shear mixer at 8000-12000 rpm and shear until they are fully mixed.

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 dichloromethane is 1:(45-55); the mass ratio of the dripped acetone to dichloromethane is 1:(0.5-0.8).

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