CN113214620B - Preparation method and application of epoxy group organic modified montmorillonite - Google Patents

Preparation method and application of epoxy group organic modified montmorillonite Download PDF

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CN113214620B
CN113214620B CN202110568919.0A CN202110568919A CN113214620B CN 113214620 B CN113214620 B CN 113214620B CN 202110568919 A CN202110568919 A CN 202110568919A CN 113214620 B CN113214620 B CN 113214620B
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montmorillonite
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epoxy group
quaternary ammonium
ammonium salt
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CN113214620A (en
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余鹏
张�杰
田瑶
吕若昀
赵西坡
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Hubei University of Technology
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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Abstract

The invention discloses a preparation method and application of epoxy group organic modified montmorillonite, wherein the preparation method comprises the following steps: (1) dissolving epoxy chloropropane in an organic solvent, adding long-chain tertiary amine, and performing addition reaction to obtain epoxy quaternary ammonium salt; (2) dispersing natural montmorillonite in deionized water to obtain montmorillonite suspension; (3) dissolving epoxy quaternary ammonium salt in deionized water to obtain epoxy quaternary ammonium salt solution; (4) dropwise adding epoxy quaternary ammonium salt solution into the montmorillonite suspension, and modifying montmorillonite through ion exchange reaction to obtain an initial product; (5) and centrifuging, washing, drying and refining the primary product to obtain the powdery epoxy group organic modified montmorillonite. The organic modified montmorillonite prepared by the invention has larger interlayer spacing and simultaneously has active epoxy groups, can improve the dispersibility of the montmorillonite in a biodegradable polyester blending system, and better plays roles in compatibilization and reinforcement.

Description

Preparation method and application of epoxy group organic modified montmorillonite
Technical Field
The invention belongs to the field of nano composite material preparation, and particularly relates to a preparation method of epoxy group organic modified montmorillonite.
Background
Montmorillonite is a layered silicate natural mineral, and has abundant reserves in the crust and wide application fields. The surface of the silicate sheet layer is negatively charged, a large number of cations are adsorbed between layers, and the cations are accumulated into clusters under the electrostatic action between the layers. The special lamellar structure determines the unique properties of the montmorillonite, such as larger specific surface area, good ion exchange capacity, hydrophilic and oleophobic properties and the like. As a silicate inorganic filler, the hydrophilic and oleophobic properties of montmorillonite limit the application of montmorillonite in polymer, but the special structure of montmorillonite endows montmorillonite with huge organic modification potential.
In order to increase the interlayer distance of montmorillonite and facilitate the insertion of polymer molecular chains, the montmorillonite is generally organically modified by using a cationic modifier such as quaternary ammonium salt with long-chain alkyl, quaternary phosphonium salt and the like. The modified montmorillonite is well dispersed in a part of polymer system. Chinese patent publication No. CN110079019A discloses a toughened and modified PA-PP (nylon-polypropylene) mixed resin material and a preparation method thereof, wherein a rare earth coupling agent is used to modify the surface of montmorillonite, and then the modified montmorillonite is introduced into polypropylene melt-grafted maleic anhydride to improve the compatibility and mechanical properties of the blend.
Generally speaking, in order to achieve the effects of compatibilization and reinforcement, the modified montmorillonite needs to have larger interlayer spacing on one hand, so that the polymer molecular chain is conveniently inserted; on the other hand, interaction with the polymer matrix is required. In order to achieve the purpose, montmorillonite is often required to be modified for multiple times or other bulking agents are added during processing, and the process is complicated. Moreover, the existing modified montmorillonite has poor dispersibility in biodegradable polyester systems such as polylactic acid and the like, and has unobvious compatibilization enhancing effect and lacks industrial application potential.
Disclosure of Invention
In order to solve the problems pointed out by the background technology, the invention provides a preparation method and application of epoxy group organic modified montmorillonite.
The invention provides a preparation method of epoxy group organic modified montmorillonite, which comprises the following steps:
(1) dissolving epoxy chloropropane in an organic solvent, adding long-chain tertiary amine, and carrying out addition reaction to obtain epoxy quaternary ammonium salt;
(2) dispersing natural montmorillonite in deionized water to obtain montmorillonite suspension;
(3) dissolving epoxy quaternary ammonium salt in deionized water to obtain epoxy quaternary ammonium salt solution;
(4) dropwise adding epoxy quaternary ammonium salt solution into the montmorillonite suspension, and modifying montmorillonite through ion exchange reaction to obtain an initial product;
(5) and centrifuging, washing, drying and refining the primary product to obtain the powdery epoxy group organic modified montmorillonite.
The organic solvent for dissolving epichlorohydrin in the present invention is not particularly limited as long as the organic solvent can dissolve epichlorohydrin and does not react with the long-chain tertiary amine, and examples of the organic solvent include ethanol, methanol, and a mixed solvent of the two. In the invention, the rotation speed of stirring in the step (1) is 100-500 r/min, and the rotation speed of stirring in the step (4) is 200-1000 r/min.
The epoxy value of the epoxy group organic modified montmorillonite prepared by the invention is 1mol/100 g-10 mol/100g, and the epoxy value refers to the amount of epoxy group substances in every 100g of the epoxy group organic modified montmorillonite.
In the step (1), the reaction temperature is preferably 60-70 ℃, the reaction time is preferably 3-5 h, and the molar ratio of epoxy chloropropane to long-chain tertiary amine is preferably 1.2: 1-1.5: 1.
Preferably, the natural montmorillonite is one or a combination of sodium montmorillonite and calcium montmorillonite.
Further, the long-chain tertiary amine is tertiary amine with one or more long-chain alkyl groups; the long-chain tertiary amine is preferably C12～C18Alkyldimethyl tertiary amines, for example, combinations of one or more of dodecyldimethyl tertiary amine, tetradecyldimethyl tertiary amine, hexadecyldimethyl tertiary amine, and octadecyldimethyl tertiary amine; also can be dioctadecylmethyl tertiary amine.
Further, in the step (1), the mixed solution obtained by the reaction is subjected to reduced pressure distillation and washing to obtain the epoxy quaternary ammonium salt.
In the step (4), the dosage of the epoxy quaternary ammonium salt is preferably 1-5 times of the cation exchange capacity of the montmorillonite, the modification reaction temperature is preferably 60-70 ℃, and the further preference is 65 ℃; the reaction time is preferably 5 to 7 hours, and more preferably 6 hours. Furthermore, the refinement in the step (5) is to refine the grain diameter of the epoxy group organic modified montmorillonite to 18-74 μm.
The application of the prepared epoxy group organic modified montmorillonite provided by the invention is as follows: the epoxy group organic modified montmorillonite is added into a biodegradable polyester system by a melt blending mode.
The amount of the epoxy group-organically-modified montmorillonite added is preferably 0.5 to 1.5 wt%, more preferably 1.0 wt%.
Further, the biodegradable polyester is a biodegradable polyester containing a terminal hydroxyl group or a terminal carboxyl group, and is preferably one or a mixture of polylactic acid, polycaprolactone, polyglycolic acid, polyethylene glycol succinate and polybutylene succinate.
Compared with the prior art, the invention has the following main advantages and beneficial effects:
(1) the process is simple and easy to implement, the organic modified montmorillonite which has larger interlayer spacing and simultaneously has active epoxy groups can be obtained by one-step modification, and the cost is lower.
(2) The active epoxy group carried by the obtained organic modified montmorillonite can improve the dispersibility of the montmorillonite in a biodegradable polyester system through the reaction with the carboxyl-terminated group, the hydroxyl-terminated group and other groups in a polymer molecular chain, and better plays roles in compatibilization and reinforcement.
Drawings
FIG. 1 is an infrared spectrum of Na-MMT (natural Na-montmorillonite) and OMMT (epoxy group organically modified montmorillonite);
FIG. 2 is an X-ray diffraction pattern of Na-MMT, OMMT and composite PLA/PBS/OMMT;
FIG. 3 is a SEM of the composite material, wherein (a) is a SEM of the composite material with Na-MMT added thereto, and (b) is a SEM of the composite material with OMMT added thereto.
Detailed Description
In order to make those skilled in the art better understand the technical solution and technical effects of the present invention, several examples will be provided below, and it is obvious that the following descriptions are only examples, which do not limit the scope of the present invention.
Example 1
50mL of epichlorohydrin is dissolved in 200mL of ethanol, and the temperature is raised to 60 ℃. Slowly adding dodecyl dimethyl tertiary amine, wherein the molar ratio of the epoxy chloropropane to the dodecyl dimethyl tertiary amine is 1.5:1, mechanically stirring for 3 hours at the rotating speed of 200r/min, and cooling to room temperature. And distilling the solution under reduced pressure by using a rotary evaporator, adding ethanol, and repeatedly washing for three times to obtain a light yellow paste, namely the epoxy quaternary ammonium salt.
2g of sodium-based montmorillonite having a cation exchange capacity of 100meq/100g (meq/100g is a unit of cation exchange capacity, 1meq/100g means that each gram of sodium-based montmorillonite contains 1mmol of exchangeable Na+Ion), adding 250mL of deionized water, and performing ultrasonic dispersion to prepare montmorillonite suspension. 2.5g of epoxy quaternary ammonium salt is dissolved in 50mL of deionized water and slowly added into the montmorillonite suspension in a dropwise manner. The temperature is increased to 65 ℃, the mixture is mechanically stirred for 6 hours at the rotating speed of 500r/min, and the yellow montmorillonite suspension gradually turns white. And centrifugally separating the mixed solution at 7000r/min, detecting by using a silver nitrate reagent, washing until no chloride ions exist, carrying out vacuum drying at 80 ℃ for 24h, grinding and sieving by using a 500-mesh sieve to obtain white powdery epoxy group organic modified montmorillonite.
Adding 1 wt% of epoxy group organic modified montmorillonite into a polylactic acid/polybutylene succinate system with the mass ratio of 80:20, and testing the obtained composite material. In addition, 1 wt% of unmodified montmorillonite was added to a polylactic acid/polybutylene succinate system at a mass ratio of 80:20 as a comparative example, and the same test was performed on the resulting composite material. XRD shows that the interlayer spacing of the modified montmorillonite in the embodiment is enlarged to 4.41nm, and the interlayer spacing of the unmodified montmorillonite is unchanged to 1.25nm in the composite material. The scanning electron microscope shows that the size of the dispersed phase in the composite material is smaller and the distribution is more uniform. Meanwhile, compared with the comparative example, the tensile strength of the composite material added with the dodecyl dimethyl epoxy group organic modified montmorillonite is increased from 38.55MPa to 51.92MPa, and the impact strength is increased from 1.65kJ/m2Increased to 2.17kJ/m2。
Example 2
50mL of epichlorohydrin is dissolved in 200mL of ethanol, and the temperature is raised to 65 ℃. Slowly adding tetradecyl dimethyl tertiary amine, wherein the molar ratio of the epoxy chloropropane to the tetradecyl dimethyl tertiary amine is 1.3:1, mechanically stirring at the rotating speed of 200r/min for 4h, and cooling to room temperature. And (3) carrying out reduced pressure distillation on the solution by using a rotary evaporator, adding ethanol, and repeatedly washing for three times to obtain a light yellow paste, namely the epoxy quaternary ammonium salt.
Taking 2g of sodium-based montmorillonite with the cation exchange capacity of 100meq/100g, adding 250mL of deionized water, and performing ultrasonic dispersion to obtain montmorillonite suspension. 2g of epoxy quaternary ammonium salt is dissolved in 50mL of deionized water and slowly added into the montmorillonite suspension in a dropwise manner. The temperature is increased to 65 ℃, the mixture is mechanically stirred for 6 hours at the rotating speed of 500r/min, and the yellow montmorillonite suspension gradually turns white. And centrifugally separating the mixed solution at 7000r/min, detecting by using a silver nitrate reagent, washing until no chloride ions exist, carrying out vacuum drying at 80 ℃ for 24h, grinding and sieving by using a 500-mesh sieve to obtain white powdery epoxy group organic modified montmorillonite.
Adding 1 wt% of epoxy group organic modified montmorillonite into a polylactic acid/polybutylene succinate system with the mass ratio of 80:20, and testing the obtained composite material. In addition, 1 wt% of unmodified montmorillonite was added to a polylactic acid/polybutylene succinate system at a mass ratio of 80:20 as a comparative example, and the same test was performed on the resulting composite material. XRD shows that the interlamellar spacing of the modified montmorillonite in the embodiment is enlarged to 4.67nm, and the interlamellar spacing of the unmodified montmorillonite is unchanged to 1.25nm in the composite material. Scanning electron microscopy shows that the size of the dispersed phase in the composite material in the embodiment is smaller, and the dispersed phase is more uniformly distributed. Meanwhile, compared with the comparative example, the tensile strength of the composite material added with the tetradecyl dimethyl epoxy group organic modified montmorillonite is increased from 38.55MPa to 53.31MPa, and the impact strength is increased from 1.65kJ/m2Increased to 2.66kJ/m2。
Example 3
50mL of epichlorohydrin is taken and dissolved in 200mL of ethanol, and the temperature is raised to 70 ℃. Slowly adding octadecyl dimethyl tertiary amine with the mol ratio of the epoxy chloropropane to the octadecyl dimethyl tertiary amine of 1.2:1, mechanically stirring at the rotating speed of 200r/min for 5h, and cooling to room temperature. And (3) carrying out reduced pressure distillation on the solution by using a rotary evaporator, adding ethanol, and repeatedly washing for three times to obtain a light yellow paste, namely the epoxy quaternary ammonium salt.
Taking 2g of sodium-based montmorillonite with the cation exchange capacity of 100meq/100g, adding 250mL of deionized water, and performing ultrasonic dispersion to obtain montmorillonite suspension. Dissolving 1.5g of epoxy quaternary ammonium salt in 50mL of deionized water, slowly dripping the epoxy quaternary ammonium salt into the montmorillonite suspension, heating to 65 ℃, mechanically stirring at the rotating speed of 500r/min for 6 hours, and gradually whitening the yellow montmorillonite suspension. And centrifugally separating the mixed solution at 7000r/min, detecting by using a silver nitrate reagent, washing until no chloride ions exist, carrying out vacuum drying at 80 ℃ for 24h, grinding and sieving by using a 500-mesh sieve to obtain white powdery epoxy group organic modified montmorillonite.
0.5 wt% of epoxy group organic modified montmorillonite is added into a polylactic acid/polybutylene succinate system with the mass ratio of 80:20, and the obtained composite material is tested. In addition, 0.5 wt% of unmodified montmorillonite was added to a polylactic acid/polybutylene succinate system at a mass ratio of 80:20 as a comparative example, and the same test was performed on the resulting composite material. XRD shows that the interlayer spacing of the modified montmorillonite in the embodiment is enlarged to 5.09nm, and the interlayer spacing of the unmodified montmorillonite is unchanged to 1.25nm in the composite material. Scanning electron microscopy shows that the size of the dispersed phase of the composite material in the embodiment is smaller, and the distribution is more uniform. Meanwhile, compared with the comparative example, the tensile strength of the composite material added with the octadecyl dimethyl epoxy group organic modified montmorillonite is increased from 37.25MPa to 59.55MPa, and the impact strength is increased from 1.46kJ/m2Increased to 2.56kJ/m2。
Example 4
50mL of epichlorohydrin is dissolved in 200mL of ethanol, and the temperature is raised to 70 ℃. Slowly adding octadecyl dimethyl tertiary amine with the mol ratio of the epoxy chloropropane to the octadecyl dimethyl tertiary amine of 1.2:1, mechanically stirring at the rotating speed of 200r/min for 5h, and cooling to room temperature. And (3) carrying out reduced pressure distillation on the solution by using a rotary evaporator, adding ethanol, and repeatedly washing for three times to obtain a light yellow paste, namely the epoxy quaternary ammonium salt.
Taking 2g of sodium-based montmorillonite with the cation exchange capacity of 100meq/100g, adding 250mL of deionized water, and performing ultrasonic dispersion to obtain montmorillonite suspension. Dissolving 1.5g of epoxy quaternary ammonium salt in 50mL of deionized water, slowly dropwise adding the epoxy quaternary ammonium salt into the montmorillonite suspension, heating to 65 ℃, mechanically stirring at the rotating speed of 500r/min for 6 hours, and gradually whitening the yellow montmorillonite suspension. And centrifugally separating the mixed solution at 7000r/min, detecting by using a silver nitrate reagent, washing until no chloride ions exist, carrying out vacuum drying at 80 ℃ for 24h, grinding and sieving by using a 500-mesh sieve to obtain white powdery epoxy group organic modified montmorillonite.
To a mass ratio ofAnd (3) adding 1 wt% of epoxy group organic modified montmorillonite into a polylactic acid/polybutylene succinate system at a ratio of 80:20, and testing the obtained composite material. In addition, 1 wt% of unmodified montmorillonite was added to a polylactic acid/polybutylene succinate system at a mass ratio of 80:20 as a comparative example, and the same test was performed on the resulting composite material. XRD shows that the interlayer spacing of the epoxy group organically modified montmorillonite in the composite material is enlarged to 5.25nm, and the interlayer spacing of the unmodified montmorillonite is unchanged to 1.25 nm. Scanning electron microscopy shows that the size of the dispersed phase of the composite material in the embodiment is smaller, and the distribution is more uniform. Meanwhile, compared with the comparative example, the tensile strength of the composite material added with the octadecyl dimethyl epoxy group organic modified montmorillonite is increased from 38.55MPa to 62.48MPa, and the impact strength of the composite material is increased from 1.65kJ/m2Increased to 3.01kJ/m2。
Example 5
50mL of epichlorohydrin is dissolved in 200mL of ethanol, and the temperature is raised to 70 ℃. Slowly adding octadecyl dimethyl tertiary amine with the mol ratio of the epoxy chloropropane to the octadecyl dimethyl tertiary amine of 1.2:1, mechanically stirring at the rotating speed of 200r/min for 5h, and cooling to room temperature. And (3) carrying out reduced pressure distillation on the solution by using a rotary evaporator, adding ethanol, and repeatedly washing for three times to obtain a light yellow paste, namely the epoxy quaternary ammonium salt.
Taking 2g of sodium-based montmorillonite with the cation exchange capacity of 100meq/100g, adding 250mL of deionized water, and performing ultrasonic dispersion to obtain montmorillonite suspension. Dissolving 1.5g of epoxy quaternary ammonium salt in 50mL of deionized water, slowly dropwise adding the epoxy quaternary ammonium salt into the montmorillonite suspension, heating to 65 ℃, mechanically stirring at the rotating speed of 500r/min for 6 hours, and gradually whitening the yellow montmorillonite suspension. And centrifugally separating the mixed solution at 7000r/min, detecting by using a silver nitrate reagent, washing until no chloride ions exist, carrying out vacuum drying at 80 ℃ for 24h, grinding and sieving by using a 500-mesh sieve to obtain white powdery epoxy group organic modified montmorillonite.
Adding 1.5 wt% of epoxy group organic modified montmorillonite into a polylactic acid/polybutylene succinate system with the mass ratio of 80:20, and testing the obtained composite material. In addition, the polylactic acid/polybutylene succinate system with the mass ratio of 80:20 is added1.5 wt% of unmodified montmorillonite was added as a comparative example. XRD shows that the interlayer spacing of the epoxy group organically modified montmorillonite in the composite material is enlarged to 5.38nm, and the interlayer spacing of unmodified montmorillonite is unchanged to 1.25 nm. Scanning electron microscopy shows that the size of the dispersed phase of the composite material in the embodiment is smaller, and the distribution is more uniform. Meanwhile, compared with the comparative example, the composite material added with the octadecyl dimethyl epoxy group organic modified montmorillonite has the tensile strength increased from 36.25MPa to 57.01MPa, and the impact strength increased from 1.38kJ/m2Increased to 1.82kJ/m2。
Table 1 shows the performance parameters of the epoxy group organically modified montmorillonite prepared in examples 1-5. As can be seen from the table, the longer the carbon chain of the tertiary amine alkyl used in the modification of montmorillonite, the more obvious the interlayer distance of montmorillonite is enlarged. The modified montmorillonite can form an intercalation structure in the polymer, and an epoxy group on the modified montmorillonite reacts with a terminal hydroxyl group or a terminal carboxyl group of a polymer molecular chain to hinder the movement of the molecular chain and the aggregation of a disperse phase, so that the compatibility degree and the mechanical strength of the composite material can be improved. The compatibilization and enhancement effects of the modified montmorillonite are related to the addition amount of the montmorillonite, and when the addition amount of the montmorillonite is too much, local agglomeration is easily caused, so that stress concentration is caused, and the overall performance of the material is reduced. For the montmorillonite prepared by the process, the addition amount of the epoxy group organic modified montmorillonite can be 0.5 wt% -1.5 wt%, 0.5 wt% -1 wt%, 1 wt% -1.5 wt%, preferably 0.5 wt% -1 wt%, and more preferably 1 wt%, and when the addition amount is 1 wt% in a polylactic acid/polybutylene succinate system, the composite material has the most excellent comprehensive performance.
TABLE 1 Performance parameters of epoxy group organically modified montmorillonite prepared in examples 1 to 5
Figure BDA0003081887510000061
Referring to FIG. 1, there is shown a comparison of the infrared spectra of Na-MMT and OMMT prepared in examples 3-4. As can be seen from the figure, in the infrared spectrum of Na-MMT, 3655cm-1Asymmetric stretching of-OH as free waterPeak of vibration absorption, 3458cm-1Is a-OH asymmetric stretching vibration absorption peak of 1640cm on the surface of montmorillonite-1Bending vibration absorption Peak of-OH, 1040cm-1、800cm-1、460cm-1Respectively are the stretching, bending and swinging vibration absorption peaks of the Si-O-Si framework in the montmorillonite silicate framework. In the infrared spectrum of OMMT, the-OH asymmetric stretching vibration absorption peak of free water disappears; 2920cm-1Of (C is a-CH)3And 2850cm-1Of (C is a-CH)2-the extension vibration absorption peak is marked with an organic modifier which is successfully inserted between montmorillonite layers; 1392cm-1The absorption peak of C-N stretching vibration exists and slightly shifts to the right, which also indicates that the quaternary ammonium salt is inserted into the interlayer of the montmorillonite. In addition, 1240cm-1Has an expansion and contraction vibration absorption peak of 908cm of epoxy group-1The bending vibration absorption peak of the epoxy group exists, which shows that the epoxy group exists on the modified montmorillonite.
Referring to FIG. 2, X-ray diffraction patterns of Na-MMT, OMMT prepared in examples 3-4 and PLA/PBS/OMMT composite material prepared in example 4 are shown, wherein the PLA/PBS/OMMT composite material is obtained by adding OMMT to a PLA/PBS system (polylactic acid/polybutylene succinate system), the mass ratio of PLA to PBS in the PLA/PBS is 80:20, and the addition amount of OMMT is 1 wt%. As can be seen from the figure, the d of the unmodified Na-MMT001Layer spacing of 1.25nm, epoxy group organic modified montmorillonite OMMT d001The interlayer spacing reaches 2.13nm, and OMMT is applied to PLA/PBS system, and d of OMMT001The interlayer spacing was further expanded to 5.38 nm. This indicates that the epoxy quaternary ammonium salt has been successfully inserted between the montmorillonite layers, and in the PLA/PBS system, the polymer molecular chain is further inserted between the montmorillonite layers.
Referring to fig. 3, which shows a scanning electron micrograph of the composite material, in (a), Na — MMT is added to a mass ratio of 80:20 of a PLA/PBS system; and (b) the composite material obtained by adding OMMT into a PLA/PBS system with the mass ratio of 80:20, wherein the adding amount of Na-MMT and the adding amount of OMMT are both 1 wt%, and the surface appearance of the composite material can be reflected by the electron microscope picture. As can be seen from the figure, the dispersed phase of the composite material added with Na-MMT is large, and the average particle size is about 3.31 μm. The composite material with the OMMT added has smaller dispersed phase, average grain size of about 0.96 μm and homogeneous dispersed phase distribution.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to be construed in all aspects and as broadly as possible, and all changes, equivalents and modifications that fall within the true spirit and scope of the invention are therefore intended to be embraced therein.

Claims (5)

1. A preparation method of epoxy group organic modified montmorillonite is characterized by comprising the following steps:
(1) dissolving epoxy chloropropane in an organic solvent, adding long-chain tertiary amine, and carrying out addition reaction to obtain epoxy quaternary ammonium salt;
(2) dispersing natural montmorillonite in deionized water to obtain montmorillonite suspension;
(3) dissolving epoxy quaternary ammonium salt in deionized water to obtain epoxy quaternary ammonium salt solution;
(4) dropwise adding epoxy quaternary ammonium salt solution into the montmorillonite suspension, and modifying montmorillonite through ion exchange reaction to obtain an initial product;
(5) centrifuging, washing, drying and refining the primary product to obtain powdery epoxy group organic modified montmorillonite;
in the step (1), the mol ratio of epoxy chloropropane to long-chain tertiary amine is 1.2: 1-1.5: 1;
in the step (4), the dosage of the epoxy quaternary ammonium salt is 1-5 times of the cation exchange capacity of the natural montmorillonite;
the long-chain tertiary amine is C12～C18An alkyl dimethyl tertiary amine;
the natural montmorillonite is sodium montmorillonite.
2. The method for preparing epoxy group organically modified montmorillonite as claimed in claim 1, wherein:
in the step (1), the reaction temperature is 60-70 ℃, and the reaction time is 3-5 h.
3. The method for preparing epoxy group organically modified montmorillonite as claimed in claim 1, wherein:
in the step (4), the modification reaction temperature is 60-70 ℃, and the reaction time is 5-7 h.
4. The application of the epoxy group organically modified montmorillonite prepared according to any one of claims 1 to 3 is characterized in that:
the epoxy group organic modified montmorillonite is added into a biodegradable polyester blending system in a melt blending mode to obtain the reinforced composite material.
5. The use as claimed in claim 4, wherein:
the addition amount of the epoxy group organic modified montmorillonite is 0.5 wt% -1.5 wt%.
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EP1762250A1 (en) * 2005-09-12 2007-03-14 Fresenius Kabi Deutschland GmbH Conjugates of hydroxyalkyl starch and an active substance, prepared by chemical ligation via thiazolidine
CN101717090A (en) * 2009-12-07 2010-06-02 上海工程技术大学 Hyperbranched quaternary ammonium salt modified organo montmorillonite and preparation method thereof
CN105237974B (en) * 2015-10-09 2018-06-26 湖北工业大学 A kind of in-situ polymerization PLA/MMT degradations enhancing masterbatch and preparation method thereof
CN110183773B (en) * 2019-07-03 2021-06-25 西北师范大学 Preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material

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