CN112048195A - Method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt - Google Patents
Method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt Download PDFInfo
- Publication number
- CN112048195A CN112048195A CN202010772096.9A CN202010772096A CN112048195A CN 112048195 A CN112048195 A CN 112048195A CN 202010772096 A CN202010772096 A CN 202010772096A CN 112048195 A CN112048195 A CN 112048195A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- quaternary ammonium
- ammonium salt
- erucamide
- propyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/42—Clays
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a method for modifying montmorillonite by erucyl propyl quaternary ammonium salt, which comprises the steps of firstly modifying the montmorillonite by adopting inorganic acid to enable the montmorillonite to generate rich O-Al broken bonds, then enabling erucyl propyl quaternary ammonium salt cationic surfactant, hexadecyl or octadecyl quaternary ammonium salt cationic surfactant and erucyl amide nonionic surfactant to react with the montmorillonite modified by the inorganic acid in an isopropanol water solution, and chemically and physically adsorbing erucyl propyl quaternary ammonium cation, alkyl quaternary ammonium cation and erucyl amide on the inner and outer surfaces of montmorillonite particles through electrostatic action, coordination action and intermolecular action to obtain the modified montmorillonite; the organic montmorillonite prepared by the invention has adjustable hydrophobicity and good thermal stability, can be used as an oil paint dispersant and an anti-settling agent, has good compatibility with resin, and can be applied to high polymers by utilizing the lubricity, the plasticity and the like of the organic montmorillonite.
Description
Technical Field
The invention relates to a method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt.
Background
Montmorillonite is a cationic layered aluminosilicate nonmetallic mineral, and the laminated plate consists of two Si-O tetrahedral wafers and Al-O octahedral wafers. With some Al in octahedron3+Can be coated with Mg2+By substitution of some Si in tetrahedron4+Is covered with Al3+Displacement produces a permanent negative charge. Therefore, cation adsorption is required between layers of montmorillonite to achieve charge balance. Between the natural montmorillonite layers, hydrated metal cations, such as hydrated sodium ions, hydrated calcium ions, etc., are generally adsorbed. The metal cations between these layers can be replaced by other cations by ion exchange. The inorganic montmorillonite is hydrophilic, and can be organically modified through interlayer cation exchange, physical adsorption or surface grafting to increase the lipophilicity, so that the quality of the organic montmorillonite is improved, and the organic montmorillonite can meet the application requirements of different polarities in organic media and high polymers.
Alkyl quaternary ammonium salt cationic surfactants, such as cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride, are commonly used as organic intercalating agents to organically modify montmorillonite by ion exchange. The quaternary alkyl ammonium salt is adsorbed by montmorillonite by electrostatic action and intermolecular action. In such organically modified smectites, the intercalated modifier is not easily desorbed. However, quaternary ammonium cations are not sufficiently hydrophilic to resist settling and disperse in organic media.
Erucamide is one of the most important derivatives of erucic acid, is a nonionic surfactant, has a higher melting point, and has more excellent thermal stability (stability at 273 ℃) compared with oleamide. The erucamide ultra-long carbon chain structure endows the erucamide with excellent surface performance, so that the erucamide ultra-long carbon chain structure has wide application in the fields of petroleum, chemical industry, paper making, printing ink, textile, lubricating oil, mechanical processing (demoulding) food packaging and the like, and has special significance for the plastic industry. It is an anti-caking agent, a lubricant, a release agent and a plasticizer with excellent performance in a high molecular polymer material. It can also be used as surface finishing agent of wax-glazed paper, metal friction-reducing agent, corrosion inhibitor and additive for rubber and paint. Because of its non-toxicity, it is approved for wide application in food packaging plastic products.
Weekly et al (Chun Hui Zhou, Cun Jun Li, wild P. gates, et al, Co-interaction of organic locations/amine molecules in o monomethylmalonates with tunable reactivity and swellability, Applied Clay Science 179(2019)105157) modified montmorillonite with erucamide, oleamide and octadecyl trimethyl ammonium chloride. When montmorillonite is modified with only erucamide or oleamide, it is found that erucamide, oleamide can only be physically adsorbed on the outer surface of montmorillonite because erucamide, oleamide are nonionic surfactants and cannot enter into the montmorillonite interlamination by ion exchange. When the montmorillonite is modified by erucamide or oleamide and octadecyl quaternary ammonium salt simultaneously, cationic octadecyl quaternary ammonium salt is intercalated between montmorillonite layers through ion exchange, and simultaneously, because hydrophobic interaction exists between carbon chains of octadecyl quaternary ammonium salt intercalated between the montmorillonite layers and carbon chains of erucamide or oleamide, a small part of erucamide is carried between the montmorillonite layers, and most of the erucamide is physically adsorbed on the outer surface of montmorillonite particles through intermolecular force. Erucamide physically adsorbed on the outer surface of montmorillonite is easily desorbed and unstable due to weak intermolecular force. In addition, the surface of the montmorillonite particles adsorbs excessive erucamide, and the erucamide is easy to agglomerate, so that the dispersion stability in an organic medium is reduced.
The erucic acid amido propyl quaternary ammonium salt is a derivative of erucic acid amide, is a cationic surfactant, has excellent functions of emulsification, wetting, antistatic property, biodegradability and the like, and can be used for softening agents of textiles, emulsion conditioning of hair conditioner cosmetics, asphalt emulsion and waterproof coating emulsification, glass fiber softening processing, oil field auxiliaries and the like.
The montmorillonite is modified by inorganic acid and erucic acid amido propyl quaternary ammonium salt, so that the modified montmorillonite has the advantages of alkyl quaternary ammonium salt cationic surfactant and erucic acid amide nonionic surfactant. Can be used as dispersant and anti-settling agent for oil paint, has good compatibility with resin, and can be applied to high polymer by utilizing the lubricity, plasticity and the like of the resin.
Disclosure of Invention
The invention aims to provide a method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt. Firstly, inorganic acid is adopted to modify the montmorillonite, so that the montmorillonite generates rich O-Al broken bonds. Then in an isopropanol water solution, enabling erucyl propyl quaternary ammonium salt cationic surfactant, hexadecyl or octadecyl quaternary ammonium salt cationic surfactant, erucamide nonionic surfactant and montmorillonite modified by inorganic acid to react, and chemically and physically adsorbing the erucyl propyl quaternary ammonium cation, alkyl quaternary ammonium cation and erucamide nonionic on the inner and outer surfaces of montmorillonite particles through electrostatic action, coordination action and intermolecular action, so that the binding force between the erucamide ultra-long carbon chains and the montmorillonite is increased, the desorption is reduced, and the hydrophobicity and the stability are improved.
The technical scheme of the invention is as follows:
a method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt comprises the following steps:
(1) drying montmorillonite at constant temperature of 120-150 ℃ for 12-20 h, cooling to room temperature (20-30 ℃), crushing, adding into an inorganic acid aqueous solution, uniformly dispersing, sealing, reacting at constant temperature of 30-60 ℃ for 4-10 h, cooling to room temperature, centrifuging, washing with water to neutrality, and drying (drying in an oven at 80-120 ℃ for 6-12 h) to obtain acid-modified montmorillonite;
the montmorillonite is sodium-based montmorillonite or calcium-based montmorillonite, preferably sodium-based montmorillonite; the montmorillonite has a Cation Exchange Capacity (CEC) of at least 50mmol/100 g;
the inorganic acid aqueous solution is an aqueous solution of sulfuric acid, hydrochloric acid or nitric acid, and the concentration is 1-4 mol/L;
the volume consumption of the inorganic acid aqueous solution is 5-12 mL/g based on the mass of the dried montmorillonite;
(2) preparing an isopropanol aqueous solution with the volume fraction of 20-60% by using deionized water, heating the isopropanol aqueous solution to 45-60 ℃, adding erucamidopropyl quaternary ammonium salt, erucamide and alkyl quaternary ammonium salt under the condition of constant-temperature stirring, and continuously stirring for 0.5-1 h to obtain an emulsion; uniformly mixing the acid modified montmorillonite obtained in the step (1) with the obtained emulsion, carrying out sealing reaction for 6-24 h at 30-60 ℃, then cooling to room temperature, washing with water, centrifuging, drying, crushing, and sieving with a 100-mesh sieve to obtain the erucamidopropyl quaternary ammonium salt modified montmorillonite;
the erucylamidopropyl quaternary ammonium salt is N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, N- (3-erucamide) propyl-N- (3-hydroxyl) propyl-N, N-dimethyl ammonium bromide or N- (3-erucamide) propyl-N- (3-hydroxyl) propyl-N, N-diethyl ammonium bromide;
the alkyl quaternary ammonium salt is cetyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride;
taking the exchange capacity (CEC) of montmorillonite as a unit, wherein the ratio of the using amount of the erucamidopropyl quaternary ammonium salt, the using amount of the erucamide, and the using amount of the alkyl quaternary ammonium salt is 1: 0.1-0.8: 0.2-1.2;
taking the exchange capacity (CEC) of montmorillonite as a unit, wherein the sum of the using amounts of the erucamidopropyl quaternary ammonium salt, the erucamide and the alkyl quaternary ammonium salt is 1.5-3 CEC;
the volume consumption of the isopropanol aqueous solution is 10-20 mL/g based on the mass of the acid modified montmorillonite.
The invention has the beneficial effects that:
in the organically modified montmorillonite of the present invention, erucic acid amido propyl quaternary ammonium cations are intercalated between the acid modified montmorillonite layers by ion exchange, and the quaternary ammonium cations are bonded to negative charges of the montmorillonite laminate by electrostatic interaction. The montmorillonite modified by the inorganic acid contains rich O-Al broken bonds, aluminum atoms in the O-Al broken bonds have vacant orbitals, and nitrogen atoms in erucic amide groups have lone-pair electrons, so that the aluminum atoms with vacant orbitals and the nitrogen atoms with lone-pair electrons can form coordination bonds. The carbon chains in the erucamidopropyl quaternary ammonium salt are more hydrophobic than the carbon chains in the cetyl or stearyl quaternary ammonium salt, and therefore, the nonionic erucamide is more easily carried between the montmorillonite layers.
Strong electrostatic interaction and coordination bonds exist between the montmorillonite and the surfactant, and weak intermolecular force exists. Compared with single erucamide nonionic surfactant modified montmorillonite and single octadecyl/hexadecyl quaternary ammonium salt cationic surfactant modified montmorillonite, the organic montmorillonite has the advantages that the acting force between the organic montmorillonite and the modifier is enhanced, and the thermal stability is increased. In the single erucamide nonionic surfactant modified montmorillonite, only weak intermolecular force exists between the two, and because erucamide is adsorbed on the outer surface, the erucamide is too strong in hydrophobicity and easy to desorb; in the montmorillonite modified by the octadecyl/hexadecyl quaternary ammonium salt cationic surfactant, electrostatic action and intermolecular force exist between the octadecyl/hexadecyl quaternary ammonium salt cationic surfactant and the montmorillonite, and the hydrophobicity is weaker.
Thermogravimetric analysis shows that the weight loss of the traditional octadecyl/hexadecyl quaternary ammonium salt cationic surfactant modified organic montmorillonite is lower than 5 percent at 800 ℃ of 500-plus-800 ℃, and the modified organic montmorillonite belongs to structural hydroxyl, which indicates that no organic phase exists in the montmorillonite at 800 ℃ of 500-plus-800 ℃. The weight loss of the organic modified montmorillonite can reach 13% at 800 ℃ of 500-.
Detailed Description
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto.
Example 1
1. Drying 12g of calcium-based montmorillonite with Cation Exchange Capacity (CEC) of 57mmol/100g in Anji county, Zhejiang province in a constant-temperature oven at 120 deg.C for 20h, cooling to room temperature, and crushing.
2. According to the ratio of the mass (g) of montmorillonite to the volume (ml) of the inorganic acid aqueous solution of 1: and 5, mixing. Slowly adding 50mL of 1mol/L sulfuric acid solution into 10g of dried montmorillonite, uniformly stirring, sealing, reacting in an oven at the constant temperature of 30 ℃ for 4h, cooling to room temperature, centrifuging, washing with water to be neutral, and drying in the oven at the temperature of 80 ℃ for 12h to obtain the acid modified montmorillonite.
3. According to the method, 80ml of isopropanol aqueous solution with the volume fraction of 20 percent is taken, the isopropanol aqueous solution is heated to 45 ℃ according to the ratio of the mass (g) of the acid modified montmorillonite to the volume (ml) of the isopropanol aqueous solution, under the condition of constant temperature stirring, the ratio of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, erucamide and hexadecyl trimethyl ammonium bromide is 1:0.1:0.2, the sum of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of the N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, erucamide and hexadecyl trimethyl ammonium bromide is 2.99CEC, and 5g of the N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, Erucamide 0.4g and cetyl trimethyl ammonium bromide 0.8g, adding isopropanol solution, and stirring for 0.5h to obtain emulsion.
4. Adding 8g of acid modified montmorillonite into the emulsion and uniformly mixing. And (3) sealing and reacting for 6h at 30 ℃, cooling to room temperature, washing with water, centrifuging, drying, crushing and sieving to obtain the erucic acid amido propyl quaternary ammonium salt modified montmorillonite. The thermogravimetric analysis data shows that the weight loss is 9 percent at the temperature of 500-800 ℃.
Example 2
1. Placing 12g of sodium montmorillonite with a Cation Exchange Capacity (CEC) of 84mmol/100g in a constant-temperature oven at 130 ℃ for drying for 16h, cooling to room temperature, and crushing.
2. According to the ratio of the mass (g) of montmorillonite to the volume (ml) of the inorganic acid aqueous solution of 1: 7, and mixing. And slowly adding 50mL of 2mol/L hydrochloric acid solution into 10g of dried montmorillonite, uniformly stirring, sealing, reacting in an oven at the constant temperature of 40 ℃ for 6h, cooling to room temperature, centrifuging, washing with water to be neutral, and drying in the oven at the temperature of 100 ℃ for 10h to obtain the acid modified montmorillonite.
3. According to the method, 96ml of isopropanol aqueous solution with the volume fraction of 30 percent is taken according to the ratio of the mass (g) of the acid modified montmorillonite to the volume (ml) of the isopropanol aqueous solution of 1:12, the isopropanol aqueous solution is heated to 50 ℃, under the condition of constant temperature stirring, the ratio of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of N- (3-erucamide) propyl-N- (3-hydroxy) propyl-N, N-dimethyl ammonium bromide, erucamide and hexadecyl trimethyl ammonium bromide is 1:0.2:0.6, the sum of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of the N- (3-erucamide) propyl-N, N-dimethyl ammonium bromide, erucamide and hexadecyl trimethyl ammonium bromide is 2.7CEC, and the sum of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of the N- (3-erucamide) propyl-N- (3-hydroxy) propyl, 5.7g of N-dimethyl ammonium bromide, 0.7g of erucamide and 2.1g of octadecyl trimethyl ammonium chloride, adding an isopropanol solution, and continuously stirring for 45min to obtain an emulsion.
4. Adding 8g of acid modified montmorillonite into the emulsion and uniformly mixing. And (3) sealing and reacting for 10h at 40 ℃, cooling to room temperature, washing with water, centrifuging, drying, crushing and sieving to obtain the erucic acid amido propyl quaternary ammonium salt modified montmorillonite. The thermogravimetric analysis data shows that the weight loss is 12 percent at the temperature of 500-800 ℃.
Example 3
1. Placing 12g of sodium montmorillonite with Cation Exchange Capacity (CEC) of 98mmol/100g in a constant temperature oven at 140 ℃ for drying for 16h, cooling to room temperature, and crushing.
2. According to the ratio of the mass (g) of montmorillonite to the volume (ml) of the inorganic acid aqueous solution of 1: 9 and mixing. Slowly adding 90mL of 3mol/L nitric acid solution into 10g of dried montmorillonite, uniformly stirring, sealing, reacting in an oven at a constant temperature of 50 ℃ for 8h, cooling to room temperature, centrifuging, washing with water to be neutral, and drying in the oven at a temperature of 110 ℃ for 8h to obtain the acid modified montmorillonite.
3. Taking 120ml of isopropanol aqueous solution with the volume fraction of 40 percent, heating the isopropanol aqueous solution to 55 ℃, and under the condition of constant temperature stirring, taking the sum of the dosages of N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, erucamide and octadecyl trimethyl ammonium chloride (taking the exchange capacity CEC of the montmorillonite as a unit) as 1:0.6:0.8, and the sum of the dosages of N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, erucamide and octadecyl trimethyl ammonium chloride (taking the exchange capacity CEC of the montmorillonite as a unit) as 2.4CEC, and mixing 3.7g of N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, 3.4 g of N-erucamide, Erucamide 1.6g and octadecyl trimethyl ammonium chloride 2.2g, adding isopropanol solution, and stirring for 50min to obtain emulsion.
4. Adding 8g of acid modified montmorillonite into the emulsion and uniformly mixing. And (3) sealing and reacting at 50 ℃ for 12h, cooling to room temperature, washing with water, centrifuging, drying, crushing and sieving to obtain the erucic acid amido propyl quaternary ammonium salt modified montmorillonite. The thermogravimetric analysis data shows that the weight loss is 13 percent at the temperature of 500-800 ℃.
Example 4
1. Placing 12g of calcium-based montmorillonite with a Cation Exchange Capacity (CEC) of 64mmol/100g in a constant-temperature oven at 150 ℃ for drying for 12h, cooling to room temperature, and crushing.
2. According to the ratio of the mass (g) of montmorillonite to the volume (ml) of the inorganic acid aqueous solution of 1:12 and mixing. And slowly adding 120mL of 4mol/L hydrochloric acid solution into 10g of dried montmorillonite, uniformly stirring, sealing, reacting in an oven at a constant temperature of 60 ℃ for 10 hours, cooling to room temperature, centrifuging, washing with water to be neutral, and drying in the oven at a temperature of 120 ℃ for 6 hours to obtain the acid modified montmorillonite.
3. According to the method, 160ml of an isopropanol aqueous solution with the volume fraction of 60 percent is taken, the isopropanol aqueous solution is heated to 60 ℃, the ratio of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of N- (3-erucamide) propyl-N- (3-hydroxy) propyl-N, N-diethylammonium bromide, erucamide and hexadecyltrimethylammonium bromide is 1:0.8:1.2, and the sum of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of the N- (3-erucamide) propyl-N- (3-hydroxy) propyl-N, N-diethylammonium bromide, erucamide and hexadecyltrimethylammonium bromide is 1.5CEC, under the condition of constant-temperature stirring, and the mass (g) of the acid-modified montmorillonite is 1:20, the volume (ml) of the isopropanol aqueous solution is taken, and the sum of the using amounts (taking the exchange capacity CEC of the montmorillonite as a unit) of the N- (3-erucamide) propyl-N- (3-hydroxy) propyl 1.5g of N, N-diethyl ammonium bromide, 0.7g of erucamide and 1.1g of hexadecyl trimethyl ammonium bromide, adding an isopropanol solution, and continuing stirring for 1 hour to obtain an emulsion.
4. Adding 8g of acid modified montmorillonite into the emulsion and uniformly mixing. And (3) sealing and reacting for 16h at 60 ℃, cooling to room temperature, washing with water, centrifuging, drying, crushing and sieving to obtain the erucic acid amido propyl quaternary ammonium salt modified montmorillonite. The thermogravimetric analysis data shows that the weight loss is 11 percent at the temperature of 500-800 ℃.
Comparative example 1
Single hexadecyltrimethylammonium bromide modified organic montmorillonite: the literature (Renjie Ni, Yu Huang, Cheng Yao, Thermogravimetric analysis of organoclays with the said gelling surfactants, J Therm Anal Calorim (2009)96: 943-947) reports that the modified organic montmorillonite sample MMT-CTAB shows a dehydroxylation weight loss of 1.49% in the temperature range 600-710 ℃ with a cetyl trimethylammonium bromide dosage of 2.2 CEC.
Comparative example 2
Single octadecyl trimethyl ammonium bromide modified organic montmorillonite: the literature (Yunfei Xi, Zheng Ding, Hongping He, Ray L. front, Structure of organoclay-an X-Ray differentiation and thermogravimetric analysis study, Journal of Colloid and Interface Science 277(2004) 116-120) reports that the modified organic smectite sample 0.2CEC-4CEC MMT shows a dehydroxylation weight loss in the temperature range 556-636.4 ℃ of 2.13-4.539%.
Comparative example 3
A single erucamide modified montmorillonite, reported in the literature (Chun Hui Zhou, Cun Jun Li, wild P. gates, et. al, Co-interaction of organic cations/amine molecules in one monomeric inorganic phosphorus with structural and cellular activity, Applied Clay Science 179(2019)105157), had a dehydroxylation weight loss of 3.2% at 500-. According to the method of the document, single erucamide modified montmorillonite is synthesized, and when the dosage of erucamide is 0.5CEC, 1.25CEC and 1.75CEC, the dehydroxylation weight loss of a modified organic montmorillonite sample at 700 ℃ of 500-minus-plus-minus-plus is respectively 3.4%, 4.3% and 3.8%.
Claims (7)
1. A method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt is characterized by comprising the following steps:
(1) drying montmorillonite at constant temperature of 120-150 ℃ for 12-20 h, cooling to room temperature, crushing, adding into an inorganic acid aqueous solution, uniformly dispersing, sealing, reacting at constant temperature of 30-60 ℃ for 4-10 h, cooling to room temperature, centrifuging, washing with water to neutrality, and drying to obtain acid-modified montmorillonite;
(2) preparing an isopropanol aqueous solution with the volume fraction of 20-60% by using deionized water, heating the isopropanol aqueous solution to 45-60 ℃, adding erucamidopropyl quaternary ammonium salt, erucamide and alkyl quaternary ammonium salt under the condition of constant-temperature stirring, and continuously stirring for 0.5-1 h to obtain an emulsion; uniformly mixing the acid modified montmorillonite obtained in the step (1) with the obtained emulsion, carrying out sealing reaction for 6-24 h at 30-60 ℃, then cooling to room temperature, washing with water, centrifuging, drying, crushing, and sieving with a 100-mesh sieve to obtain the erucamidopropyl quaternary ammonium salt modified montmorillonite;
the erucylamidopropyl quaternary ammonium salt is N- (3-erucamide) propyl-N, N, N-trimethyl ammonium chloride, N- (3-erucamide) propyl-N- (3-hydroxyl) propyl-N, N-dimethyl ammonium bromide or N- (3-erucamide) propyl-N- (3-hydroxyl) propyl-N, N-diethyl ammonium bromide;
the alkyl quaternary ammonium salt is cetyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride.
2. The method of modifying montmorillonite with erucamidopropyl quaternary ammonium salt according to claim 1, wherein in step (1), the montmorillonite is sodium-based montmorillonite or calcium-based montmorillonite; the montmorillonite has a cation exchange capacity CEC of at least 50mmol/100 g.
3. The method for modifying montmorillonite with erucylamidopropyl quaternary ammonium salt according to claim 1, wherein in the step (1), the inorganic acid aqueous solution is sulfuric acid, hydrochloric acid or nitric acid aqueous solution, and the concentration is 1-4 mol/L.
4. The method for modifying montmorillonite with erucamidopropyl quaternary ammonium salt according to claim 1, wherein in the step (1), the volume usage amount of the inorganic acid aqueous solution is 5-12 mL/g based on the mass of dried montmorillonite.
5. The method for modifying montmorillonite with erucamidopropyl quaternary ammonium salt according to claim 1, wherein in the step (2), the ratio of the dosages of the erucamidopropyl quaternary ammonium salt, erucamide and alkyl quaternary ammonium salt is 1: 0.1-0.8: 0.2-1.2, taking the exchange capacity CEC of montmorillonite as a unit.
6. The method for modifying montmorillonite with erucamidopropyl quaternary ammonium salt according to claim 1, wherein in the step (2), the sum of the amounts of the erucamidopropyl quaternary ammonium salt, erucamide and alkyl quaternary ammonium salt is 1.5-3CEC in terms of exchange capacity CEC of montmorillonite.
7. The method for modifying montmorillonite with erucamidopropyl quaternary ammonium salt according to claim 1, wherein in the step (2), the volume usage amount of the isopropanol aqueous solution is 10-20 mL/g based on the mass of the acid-modified montmorillonite.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010772096.9A CN112048195B (en) | 2020-08-04 | 2020-08-04 | Method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010772096.9A CN112048195B (en) | 2020-08-04 | 2020-08-04 | Method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112048195A true CN112048195A (en) | 2020-12-08 |
CN112048195B CN112048195B (en) | 2021-06-29 |
Family
ID=73602083
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010772096.9A Active CN112048195B (en) | 2020-08-04 | 2020-08-04 | Method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112048195B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102219231A (en) * | 2011-05-10 | 2011-10-19 | 中国地质大学(北京) | Cationic-nonionic composite organic montmorillonite and preparation method thereof |
CN104017549A (en) * | 2014-06-05 | 2014-09-03 | 浙江丰虹新材料股份有限公司 | Organic soil for oil base drilling fluids with high yield value and preparation method thereof |
CN106276939A (en) * | 2016-08-08 | 2017-01-04 | 浙江工业大学之江学院 | A kind of fatty acid amide modified method for preparing organobentonite |
CN108752632A (en) * | 2018-06-20 | 2018-11-06 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of the quaternary ammonium salt-modified nanometer organic montmorillonite of easily disperse |
-
2020
- 2020-08-04 CN CN202010772096.9A patent/CN112048195B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102219231A (en) * | 2011-05-10 | 2011-10-19 | 中国地质大学(北京) | Cationic-nonionic composite organic montmorillonite and preparation method thereof |
CN104017549A (en) * | 2014-06-05 | 2014-09-03 | 浙江丰虹新材料股份有限公司 | Organic soil for oil base drilling fluids with high yield value and preparation method thereof |
CN106276939A (en) * | 2016-08-08 | 2017-01-04 | 浙江工业大学之江学院 | A kind of fatty acid amide modified method for preparing organobentonite |
CN108752632A (en) * | 2018-06-20 | 2018-11-06 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of the quaternary ammonium salt-modified nanometer organic montmorillonite of easily disperse |
Non-Patent Citations (2)
Title |
---|
C.H. ZHOU,ET AL: ""Co-intercalation of organic cations/amide molecules into montmorillonite with tunable hydrophobicity and swellability"", 《APPLIED CLAY SCIENCE》 * |
袁萍等: ""芥酸酰胺丙基阳离子型黏弹表面活性剂的合成及其性能"", 《石油化工》 * |
Also Published As
Publication number | Publication date |
---|---|
CN112048195B (en) | 2021-06-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Alkan et al. | FTIR and zeta potential measurements of sepiolite treated with some organosilanes | |
Kostenko et al. | Bentonites with grafted aminogroups: Synthesis, protolytic properties and assessing Cu (II), Cd (II) and Pb (II) adsorption capacity | |
Mao et al. | Functional organoclays for removal of heavy metal ions from water: A review | |
Chen et al. | Characterization of anion–cationic surfactants modified montmorillonite and its application for the removal of methyl orange | |
Leroux et al. | Polymer interleaved layered double hydroxide: a new emerging class of nanocomposites | |
Wang et al. | Hybrid organic− inorganic nanocomposites formed from an epoxy polymer and a layered silicic acid (Magadiite) | |
Han et al. | Preparation and characterization of chitosan–clay nanocomposites with antimicrobial activity | |
Greesh et al. | Adsorption of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and related compounds onto montmorillonite clay | |
Zhang et al. | Crosslinked quaternized chitosan/bentonite composite for the removal of Amino black 10B from aqueous solutions | |
JPS59206469A (en) | Filler of natural oxide or silicate whose surface is denatured with organosilicate compound at least | |
Zhang et al. | Preparation of novel flame-retardant organoclay and its application to natural rubber composites | |
CN103464123B (en) | CTMAB/CPAM/ bentonite combination socket layer material preparation method | |
US6414069B1 (en) | Hybrid mixed ion clay structures for polymer nanocomposite formation | |
KR20170083009A (en) | Organic nanoclay-polymer composite and preparing method of the same | |
Lu et al. | A new approach of enhancing the shear stress of electrorheological fluids of montmorillonite nanocomposite by emulsion intercalation of poly-N-methaniline | |
Jia et al. | Organic interfacial tailoring of styrene butadiene rubber–clay nanocomposites prepared by latex compounding method | |
CN112048195B (en) | Method for modifying montmorillonite by erucic acid amido propyl quaternary ammonium salt | |
Yu et al. | Preparation of organo-montmorillonites and the relationship between microstructure and swellability | |
CN111662575A (en) | Modified bentonite for plastics and paint | |
Zidan et al. | Crosslinked poly (methacrylic acid)/organoclay nanocomposites: synthesis, characterization and methylene blue adsorption from aquatic environments | |
Vujaković et al. | Adsorption of inorganic anionic contaminants on surfactant modified minerals | |
Beisebekov et al. | Interactions of bentonite clay in composite gels of non-ionic polymers with cationic surfactants and heavy metal ions | |
Msadok et al. | Effect of cationic surfactant HDPy+ on the acidity and hydrophilicity of Tunisian clay | |
CN102220144A (en) | Preparation method of flame retardant additive | |
Nuntiya et al. | The effect of surfactant concentration on the interlayer structure of organoclay |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |