CN105585709B - The preparation method of organic amine modified montmorillonoid/polyamide nano-composite - Google Patents
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Abstract
The present invention relates to a kind of preparation methods of organic amine modified montmorillonoid/polyamide nano-composite.The present invention is that monomer of polyamide, organic amine modified montmorillonoid and pure water are added in reaction kettle and are prepared;The present invention adds in organic amine modified montmorillonoid during hydrolysis polymerization prepares polyamide in situ, can improve the mechanical property of polyamide.The present invention using the more other nanocomposites obtained using montmorillonite or nanometer additive of organic amine modified montmorillonoid there is better mechanical property to improve the raising with thermal stability, and can improve the moisture resistance of polyamide.Preparation method of the present invention directly can prepare organic amine modified montmorillonoid/polyamide nano-composite using reaction kettle one-step method, reduce production cost, material property is further enhanced without the pre-dispersed and pre-dispersed equipment of addition.
Description
Technical field
The present invention relates to a kind of preparation methods of organic amine modified montmorillonoid/polyamide nano-composite.
Background technology
Polyamide is that kind earlier is developed in engineering plastics, has many excellent performances such as high-strength, oil resistant, damping,
It is widely used in fields such as automobile, electrical equipment, mechanical part, transportation equipment, weavings.With automotive small,
The quickening of electronic electric equipment high performance, mechanical equipment lightweight process proposes higher requirement to the performance of polyamide,
Especially as structural material, need further to improve its intensity, heat resistance and cold resistance etc..
Many inorganic material, such as glass fibre, talcum, calcium carbonate, clay can serve as filler or reinforcing agent to carry
The performance of high high molecular material.The raising degree of the performance of high molecular material generally depends on the loading of filler, filler in base
Dispersion degree and the degree of orientation, filler/base body interface situation in body etc. (Macromolecules, 2011,44:3856-3861.).
In recent years, with the development of nanometer technology, polymer nanocomposites are prepared using Nano filling, are had improving material
There is unique advantage, and cause the more and more interest of researcher in terms of performance and imparting material new capability.As Japan is rich
It is compound that the scientific research personnel of field research institute, U.S. Connell and Michigan university etc. prepares polymer/montmorillnoite nano to intercalation
Material has made extensive research, wherein just including having synthesized 6/ Nano composite material of montmorillonite of nylon.Chinese Academy of Sciences's chemistry is ground
Study carefully QiZongNeng professor et al. the nano composite polymer-montmorillonoid material that takes the lead in having carried out at home research, obtained more
Item achievement has simultaneously applied for patent (CN1162470C, CN1137198C), as monomer intercalation condensation methods prepare nylon/montmorillonoid nanometer
Composite material etc. (CN 1055706C, CN 1081207C).Research has shown that, compared with pure PA6, nanometer enhancing particle can be significantly
Improve the mechanical property of PA6.Therefore, polyamide is modified using nano-particle, for improving the overall performance of material, opened up
The application range of exhibition material is of great significance.
Montmorillonite is a kind of silicate of stratiform, has many advantages, such as that raw material is easy to get, is cheap, can directly by monomer or be gathered
The piece interlayer that object is inserted into montmorillonite is closed, it is nano unit to be removed the montmorillonite of stratiform using heat of polymerization or strong shearing force,
It is evenly dispersed in polymeric matrix.The nano combined materials of montmorillonite/PA6 prepared by in-situ inserted method and melt intercalated method
Material the experiment proved that, since montmorillonite is homogeneously dispersed in nanoscale in PA6 matrixes so that the mechanical property of composite material
Be improved (petrochemical industry, 2006,35 (8):778-781);Particularly pass through the montmorillonite of organic-treating, interlamellar spacing
Expanding makes monomer or polymer be easier the expansion and stripping of piece interlayer, the further lamella of promotion montmorillonite into montmorillonite
From so that its mechanical property (tensile strength, impact strength etc.), hot property, flame retardant property all obtain different degrees of raising.
In above-mentioned preparation process, in order to enable nanometer enhancing particle and polyamide are compound, decentralized medium etc. can be often used
Nanometer enhancing particle is pre-dispersed using the progress such as high-shear emulsifying equipment, ultrasonic equipment.Preparation process needs to add other
Equipment, process are complex (CN1127534C, CN1148398C).
The present invention is directly added organic by one-step method in-situ polymerization during prepared by monomer of polyamide in-situ polymerization
Amine modified montmorillonoid without carrying out the processes such as pre-dispersed, that is, enhances the performance of polyamide material, and reduce apparatus and process mistake
Journey reduces production cost.
Invention content
The purpose of the present invention is to provide a kind of preparation sides of organic amine modified montmorillonoid/polyamide nano-composite
Method.
The present invention organic amine modified montmorillonoid/polyamide nano-composite preparation method be according to following steps into
Row:
1) is on the basis of the parts by weight of monomer of polyamide, by the monomer of polyamide of 100 parts by weight, 0.01~80 parts by weight
Organic amine modified montmorillonoid and the pure water of 0.01~80 parts by weight be added in reaction kettle and stir evenly (generally in reaction kettle
In time for being stirred be 0.5~1 hour);
2) under stirring, filling with inert gas and vacuumize process are carried out to reaction kettle for the reaction kettle of closed step 1),
Discharge the air in reaction kettle;Backward reaction kettle in be filled with inert gas, make pressure in reaction kettle for 0.01~2.5MPa,
It is 220~270 DEG C, and keep the temperature 0.5~10 that the temperature in reaction kettle is uniformly heating to temperature in 60~120 minutes by room temperature
Hour;During incubation, the pressure in reaction kettle is at the uniform velocity reduced to normal pressure, and discharges the gaseous matter in reaction kettle;It beats later
Vacuum pump is opened, vacuumize process is carried out to reaction kettle and stops stirring, inert gas is filled with into reaction kettle, is made in reaction kettle
Pressure is to normal pressure;The outlet valve for opening reaction kettle discharges into container, is cooled to room temperature, obtains organic amine modified montmorillonoid/poly-
Amide nanocomposite.
The monomer of polyamide is selected from caprolactam, butyrolactam, spicy inner formyl amine, ω-oenantholcatam, 12- lactams
One or more of.
The dispersed phase scale of organic amine modified montmorillonoid in the nanocomposite is 10~300 nanometers.
The organic amine modified montmorillonoid is prepared for commercially available organic amine modified montmorillonoid or by following methods:
On the basis of the parts by weight of organic amine, by the organic amine of 100 parts by weight, 0.01~10 parts by weight activator,
The montmorillonite of 0.01~80 parts by weight is mixed with the pure water of 1~1000 parts by weight, and is by room temperature to temperature by mixture
It 100~150 DEG C, after stopping stirring, is utilized using homogenizer stirring shearing 10~120 minutes simultaneously in temperature-rise period
Centrifuge centrifuges gained mixture 5~60 minutes, and the rotating speed of centrifuge during centrifugation is 1000~10000 turns/
Minute, lower sediment is taken, vacuum drying is carried out 12~48 hours in the vacuum drying oven for being 60~120 DEG C in temperature later, obtains
Organic amine modified montmorillonoid.
The organic amine is selected from dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, dodecyl two
Methylbenzyl ammonium chloride, dodecyl dimethyl Benzylphosphonium Bromide amine, tetradecyl benzyl dimethyl ammonium chloride, dodecyldimethylamine
Base Benzylphosphonium Bromide amine, hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide, hexadecyldimethyl benzyl ammonium allyl chloride
Change ammonium, hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride amine, hexadecyldimethyl benzyl ammonium Benzylphosphonium Bromide amine, hexadecyldimethyl benzyl ammonium allyl bromide, bromoallylene
Change ammonium, (to ethenybenzyl) 12 (or 16) alkyl dimethyl ammonium chloride, (to ethenybenzyl) 12 (or 16) alkane
Base dimethyl amine bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethyl amine bromide, octadecyl dimethyl benzyl chlorine
Change amine, octadecyl dimethyl benzyl amine bromide, octadecyl primary amine, to (vinyl benzene) trimethylammonium bromide, chlorocarbon base two
Methyl benzene methanamine, ethylenediamine, diethylenetriamine, triethylene tetramine, phthalimide, dimethylaminoethyl acrylate methyl ammonia ethyl ester,
Trimethyl ammonium chloride, to one kind in (vinyl benzene) trimethyl ammonium chloride.
The activator is in sulfuric acid, acetic acid, hydrochloric acid, sulfonic acid, trichloroacetic acid, phosphoric acid, isophthalic acid, phthalic acid
One kind.
The montmorillonite is selected from sodium-based montmorillonite, ni montmorillonite, calcium-base montmorillonite, Sodium/Calcium base montmorillonite, magnesium-based and covers
One kind in de- soil.
The commercially available organic amine modified montmorillonoid is selected from dodecyl quaternary ammonium salt, cetyl quaternary ammonium salt, octadecane
In the organic amine modified montmorillonoid that based quaternary ammonium salt, allyl based quaternary ammonium salt, acrylamide based quaternary ammonium salt, propylene ester based quaternary ammonium salt are modified
One kind.
The present invention adds in organic amine modified montmorillonoid during hydrolysis polymerization prepares polyamide in situ, can improve
The mechanical property of polyamide.The present invention is obtained using organic amine modified montmorillonoid is more other using montmorillonite or nanometer additive
Nanocomposite there is better mechanical property to improve and the raising of thermal stability, and the moisture resistance of polyamide can be improved.
Preparation method of the present invention can directly be prepared without the pre-dispersed and pre-dispersed equipment of addition using reaction kettle one-step method
Organic amine modified montmorillonoid/polyamide nano-composite is obtained, reduces production cost, material property is further carried
It is high.
Specific embodiment
Embodiment 1
1) is on the basis of the parts by weight of butyrolactam monomer, by the butyrolactam monomer of 100 parts by weight, 0.01 parts by weight
The quaternary ammonium salt-modified organic amine modified montmorillonoid of commercially available dodecyl and the pure water of 0.01 parts by weight be added in reaction kettle
And stir 0.5 hour, stir evenly all of above raw material;
2) reaction kettle of closed step 1) under stirring, carries out reaction kettle inflated with nitrogen and vacuumize process, discharge
Air in reaction kettle;Backward reaction kettle in be filled with nitrogen, make pressure in reaction kettle that will be reacted for 0.01~0.05MPa
It is 220 DEG C, and keep the temperature 10 hours that temperature in kettle was uniformly heating to temperature by room temperature in 60 minutes;During incubation, at the uniform velocity
The pressure in reaction kettle is reduced to normal pressure, and discharges the gaseous matter in reaction kettle;Vacuum pump is opened later, and reaction kettle is carried out
Vacuumize process simultaneously stops stirring, and nitrogen is filled with into reaction kettle, makes pressure in reaction kettle to normal pressure;Open going out for reaction kettle
Material valve discharges into container, is cooled to room temperature (25 DEG C), obtains organic amine modified montmorillonoid/nano combined material of polybutyrolactam
Material.
The dispersed phase scale of organic amine modified montmorillonoid in gained nanocomposite is 10~300 nanometers.
Embodiment 2
1) is on the basis of the parts by weight of caprolactam monomer, by the caprolactam monomer of 100 parts by weight, the city of 3 parts by weight
The quaternary ammonium salt-modified organic amine modified montmorillonoid of the cetyl sold and the pure water of 1 parts by weight are added in reaction kettle and stir
0.75 hour, stir evenly all of above raw material;
2) reaction kettle of closed step 1) under stirring, carries out reaction kettle inflated with nitrogen and vacuumize process, discharge
Air in reaction kettle;Backward reaction kettle in be filled with nitrogen, make pressure in reaction kettle for 0.1~1MPa, will be in reaction kettle
Temperature temperature was uniformly heating in 100 minutes by room temperature is 250 DEG C, and keep the temperature 6 hours;During incubation, it at the uniform velocity reduces
Pressure in reaction kettle discharges the gaseous matter in reaction kettle to normal pressure;Vacuum pump is opened later, reaction kettle take out true
Vacancy manages and stops stirring, and nitrogen is filled with into reaction kettle, makes pressure in reaction kettle to normal pressure;Open the outlet valve of reaction kettle
In discharging to container, room temperature (25 DEG C) is cooled to, obtains organic amine modified montmorillonoid/polycaprolactam nanocomposite.
The dispersed phase scale of organic amine modified montmorillonoid in gained nanocomposite is 10~300 nanometers.
Table one is respectively polycaprolactam and organic amine modified montmorillonoid/polycaprolactam nanocomposite with table two
Mechanical property compares and the water vapour permeability of polycaprolactam and organic amine modified montmorillonoid/polycaprolactam nanocomposite
Comparison.From experimental result as can be seen that the mechanical property of organic amine modified montmorillonoid/polycaprolactam nanocomposite obtains
To raising, heat distortion temperature is remarkably improved.It can see according to water vapour permeability Comparative result, organic amine, which is modified to cover, to be taken off
The anti humility performance of soil/polycaprolactam nanocomposite is remarkably improved.
The mechanical property pair of table one, polycaprolactam and organic amine modified montmorillonoid/polycaprolactam nanocomposite
Than
The water vapour permeability pair of table two, polycaprolactam and organic amine modified montmorillonoid/polycaprolactam nanocomposite
Than
Embodiment 3
1) is on the basis of the parts by weight of spicy inner formyl amine monomer, by the spicy inner formyl amine monomer and 80 parts by weight of 100 parts by weight
Commercially available octadecyl quaternary ammonium salt, having of being modified of allyl based quaternary ammonium salt, acrylamide based quaternary ammonium salt or propylene ester based quaternary ammonium salt
Machine amine modified montmorillonoid and the pure water of 80 parts by weight are added in reaction kettle and stir 1 hour, make all of above raw material stirring equal
It is even;
2) reaction kettle of closed step 1) under stirring, carries out reaction kettle applying argon gas and vacuumize process, discharge
Air in reaction kettle;Backward reaction kettle in be filled with argon gas, make pressure in reaction kettle for 1.5~2.5MPa, by reaction kettle
In temperature temperature was uniformly heating in 120 minutes by room temperature is 270 DEG C, and keep the temperature 0.5 hour;During incubation, at the uniform velocity
The pressure in reaction kettle is reduced to normal pressure, and discharges the gaseous matter in reaction kettle;Vacuum pump is opened later, and reaction kettle is carried out
Vacuumize process simultaneously stops stirring, and argon gas is filled with into reaction kettle, makes pressure in reaction kettle to normal pressure;Open going out for reaction kettle
Material valve discharges into container, is cooled to room temperature (25 DEG C), obtains organic amine modified montmorillonoid/nano combined material of poly capryllactam
Material.
The dispersed phase scale of organic amine modified montmorillonoid in gained nanocomposite is 10~300 nanometers.
Embodiment 4
1) is on the basis of the parts by weight of ω-oenantholcatam monomer, by the ω of 100 parts by weight-oenantholcatam monomer and 10
The organic amine modified montmorillonoid oneself prepared of parts by weight and the pure water of 10 parts by weight are added in reaction kettle and stir 1 hour,
Stir evenly all of above raw material;
2) reaction kettle of closed step 1) under stirring, carries out reaction kettle inflated with nitrogen and vacuumize process, discharge
Air in reaction kettle;Backward reaction kettle in be filled with nitrogen, make pressure in reaction kettle for 0.5~1.5MPa, by reaction kettle
In temperature temperature was uniformly heating in 90 minutes by room temperature is 240 DEG C, and keep the temperature 5 hours;During incubation, it at the uniform velocity reduces
Pressure in reaction kettle discharges the gaseous matter in reaction kettle to normal pressure;Vacuum pump is opened later, reaction kettle take out true
Vacancy manages and stops stirring, and nitrogen is filled with into reaction kettle, makes pressure in reaction kettle to normal pressure;Open the outlet valve of reaction kettle
In discharging to container, room temperature (25 DEG C) is cooled to, obtains organic amine modified montmorillonoid/poly- ω-oenantholcatam nanocomposite.
The dispersed phase scale of organic amine modified montmorillonoid in gained nanocomposite is 10~300 nanometers.
The preparation method of organic amine modified montmorillonoid prepared by described oneself is:
On the basis of the parts by weight of organic amine, by the organic amine of 100 parts by weight, the sulfuric acid of 0.01 parts by weight or acetic acid,
The sodium-based montmorillonite or ni montmorillonite of 0.01 parts by weight are mixed with the pure water of 1 parts by weight, and by mixture by room temperature extremely
Temperature is 150 DEG C, and after stopping stirring, centrifugation is utilized using homogenizer stirring shearing 10 minutes simultaneously in temperature-rise period
Machine centrifuges gained mixture 60 minutes, and the rotating speed of centrifuge during centrifugation is 1000 revs/min, removes layer and sinks
It forms sediment, vacuum drying 48 hours is carried out in the vacuum drying oven for being 60 DEG C in temperature later, obtains organic amine modified montmorillonoid.
The organic amine is selected from dodecyl trimethyl ammonium chloride, dodecyl dimethyl Benzylmagnesium chloride amine, the tetradecane
Base dimethyl benzyl ammonium chloride, hexadecyltrimethylammonium chloride, hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride amine, (to Ethenylbenzene first
Base) 12 (or 16) alkyl dimethyl amine bromides, octadecyl trimethyl ammonium chloride, octadecyl dimethyl benzyl chlorination
Amine, octadecyl primary amine, chlorocarbon base dimethyl-benzyl amine, ethylenediamine, diethylenetriamine, triethylene tetramine, phthalyl are sub-
Amine, dimethylaminoethyl acrylate methyl ammonia ethyl ester, trimethyl ammonium chloride, to one kind in (vinyl benzene) trimethyl ammonium chloride.
Embodiment 5
1) is on the basis of the parts by weight of 12- lactam monomers, by the 12- lactam monomers and 30 weight of 100 parts by weight
Part the organic amine modified montmorillonoid oneself prepared and the pure water of 5 parts by weight be added in reaction kettle and stir 0.5 hour, make with
Upper all raw materials stir evenly;
2) reaction kettle of closed step 1) under stirring, carries out reaction kettle inflated with nitrogen and vacuumize process, discharge
Air in reaction kettle;Backward reaction kettle in be filled with nitrogen, make pressure in reaction kettle for 0.1~0.5MPa, by reaction kettle
In temperature temperature was uniformly heating in 100 minutes by room temperature is 200 DEG C, and keep the temperature 4 hours;During incubation, it at the uniform velocity drops
Pressure in low reaction kettle discharges the gaseous matter in reaction kettle to normal pressure;Vacuum pump is opened later, and reaction kettle is taken out
Vacuum processing simultaneously stops stirring, and nitrogen is filled with into reaction kettle, makes pressure in reaction kettle to normal pressure;Open the discharging of reaction kettle
Valve discharges into container, is cooled to room temperature (25 DEG C), obtains organic amine modified montmorillonoid/poly- 12- lactams nanocomposites.
The dispersed phase scale of organic amine modified montmorillonoid in gained nanocomposite is 10~300 nanometers.
The preparation method of organic amine modified montmorillonoid prepared by described oneself is:
On the basis of the parts by weight of organic amine, by the organic amine of 100 parts by weight, the hydrochloric acid of 0.1 parts by weight or sulfonic acid, 0.1
The calcium-base montmorillonite of parts by weight is mixed with the pure water of 100 parts by weight, and is 120 DEG C by room temperature to temperature by mixture,
Simultaneously using homogenizer stirring shearing 60 minutes in temperature-rise period, after stopping stirring, using centrifuge by gained mixture
It centrifuges 30 minutes, the rotating speed of centrifuge during centrifugation is 5000 revs/min, takes lower sediment, is in temperature later
Vacuum drying 24 hours is carried out in 90 DEG C of vacuum drying oven, obtains organic amine modified montmorillonoid.
The organic amine is selected from dodecyl trimethyl ammonium bromide, dodecyl dimethyl Benzylphosphonium Bromide amine, the tetradecane
Base dimethyl benzyl amine bromide, cetyl trimethylammonium bromide, hexadecyldimethyl benzyl ammonium allylic bromination ammonium, cetyl two
Methylbenzyl amine bromide, (to ethenybenzyl) 12 (or 16) alkyl dimethyl amine bromide, octadecyl trimethyl bromination
Amine, octadecyl dimethyl benzyl amine bromide, to one kind in (vinyl benzene) trimethylammonium bromide.
Embodiment 6
1) is on the basis of the parts by weight of caprolactam, by oneself of the caprolactam monomer of 100 parts by weight and 10 parts by weight
The organic amine modified montmorillonoid and the pure water of 10 parts by weight that oneself prepares are added in reaction kettle and stir 1 hour, make all of above
Raw material stirs evenly;
2) reaction kettle of closed step 1) under stirring, carries out reaction kettle inflated with nitrogen and vacuumize process, discharge
Air in reaction kettle;Backward reaction kettle in be filled with nitrogen, make pressure in reaction kettle for 0.1~0.5MPa, by reaction kettle
In temperature temperature was uniformly heating in 110 minutes by room temperature is 260 DEG C, and keep the temperature 2 hours;During incubation, it at the uniform velocity drops
Pressure in low reaction kettle discharges the gaseous matter in reaction kettle to normal pressure;Vacuum pump is opened later, and reaction kettle is taken out
Vacuum processing simultaneously stops stirring, and nitrogen is filled with into reaction kettle, makes pressure in reaction kettle to normal pressure;Open the discharging of reaction kettle
Valve discharges into container, is cooled to room temperature (25 DEG C), obtains organic amine modified montmorillonoid/polycaprolactam nanocomposite.
The dispersed phase scale of organic amine modified montmorillonoid in gained nanocomposite is 10~300 nanometers.
The preparation method of organic amine modified montmorillonoid prepared by described oneself is:
On the basis of the parts by weight of dodecyl trimethyl ammonium chloride, by the trimethyl chlorination of 100 parts by weight
Ammonium, trichloroacetic acid, phosphoric acid, isophthalic acid or the phthalic acid of 10 parts by weight, the Sodium/Calcium base montmorillonite or magnesium-based of 80 parts by weight cover
De- soil is mixed with the pure water of 1000 parts by weight, and is 150 DEG C by room temperature to temperature by mixture, in temperature-rise period simultaneously
Using homogenizer stirring shearing 120 minutes, after stopping stirring, gained mixture is centrifuged 5 minutes using centrifuge,
The rotating speed of centrifuge during centrifugation is 10000 revs/min, takes lower sediment, later in the vacuum drying oven that temperature is 120 DEG C
In carry out vacuum drying 12 hours, obtain organic amine modified montmorillonoid.
Claims (8)
1. a kind of preparation method of organic amine modified montmorillonoid/polyamide nano-composite, it is characterized in that, the preparation side
Method is to follow the steps below:
1) is on the basis of the parts by weight of monomer of polyamide, and the monomer of polyamide of 100 parts by weight, 0.01~80 parts by weight are had
Machine amine modified montmorillonoid and the pure water of 0.01~80 parts by weight are added in reaction kettle and stir evenly;
2) reaction kettle of closed step 1) under stirring, carries out reaction kettle filling with inert gas and vacuumize process, discharge
Air in reaction kettle;Backward reaction kettle in be filled with inert gas, make pressure in reaction kettle for 0.01~2.5MPa, will be anti-
It is 220~270 DEG C, and it is small to keep the temperature 0.5~10 that the temperature in kettle is answered, which to be uniformly heating to temperature in 60~120 minutes by room temperature,
When;During incubation, the pressure in reaction kettle is at the uniform velocity reduced to normal pressure, and discharges the gaseous matter in reaction kettle;It opens later
Vacuum pump carries out reaction kettle vacuumize process and stops stirring, inert gas is filled with into reaction kettle, makes the pressure in reaction kettle
By force to normal pressure;The outlet valve discharging of reaction kettle is opened, room temperature is cooled to, it is multiple to obtain organic amine modified montmorillonoid/polyamide nano
Condensation material.
2. preparation method according to claim 1, it is characterized in that:The time of stirring described in step 1) is small for 0.5~1
When.
3. preparation method according to claim 1, it is characterized in that:The monomer of polyamide is in caprolactam, fourth
One or more of amide, spicy inner formyl amine, ω-oenantholcatam, 12- lactams.
4. preparation method according to claim 1, it is characterized in that:Organic amine in the nanocomposite, which is modified, to be covered
The dispersed phase scale for taking off soil is 10~300 nanometers.
5. the preparation method according to claim 1 or 4, it is characterized in that:The organic amine modified montmorillonoid is selected from ten
Dialkyl quats salt, cetyl quaternary ammonium salt, octadecyl quaternary ammonium salt, allyl based quaternary ammonium salt, acrylamide based quaternary ammonium salt, propylene
One kind in the organic amine modified montmorillonoid that ester based quaternary ammonium salt is modified;
Or the organic amine modified montmorillonoid is prepared by following methods:
On the basis of the parts by weight of organic amine, by the organic amine of 100 parts by weight, the activator of 0.01~10 parts by weight, 0.01~
The montmorillonite of 80 parts by weight is mixed with the pure water of 1~1000 parts by weight, and by mixture by room temperature to temperature for 100~
150 DEG C, after stopping stirring, centrifuge is utilized using homogenizer stirring shearing 10~120 minutes simultaneously in temperature-rise period
Gained mixture is centrifuged 5~60 minutes, the rotating speed of centrifuge during centrifugation is 1000~10000 revs/min, is taken
Lower sediment carries out vacuum drying 12~48 hours in vacuum drying oven of the temperature for 60~120 DEG C later, obtains organic amine and change
Property montmorillonite.
6. preparation method according to claim 5, it is characterized in that:The organic amine is selected from trimethyl chlorination
Ammonium, dodecyl trimethyl ammonium bromide, dodecyl dimethyl Benzylmagnesium chloride amine, dodecyl dimethyl Benzylphosphonium Bromide amine, ten
Tetraalkyl dimethyl benzyl ammonium chloride, myristyl benzyl dimethyl amine bromide, hexadecyltrimethylammonium chloride, cetyl
Trimethylammonium bromide, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, hexadecyldimethyl benzyl ammonium Benzylmagnesium chloride amine, etradecyldimethylamine
It is base Benzylphosphonium Bromide amine, hexadecyldimethyl benzyl ammonium allylic bromination ammonium, p-methylstyrene base dodecyl dimethyl ammonium chloride, right
Methyl styrene base hexadecyldimethyl benzyl ammonium ammonium chloride, p-methylstyrene base lauryl dimethyl amine bromide, to methylbenzene
Vinyl Hexadecyldimethylammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethyl amine bromide, octadecyl
Dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl amine bromide, octadecyl primary amine, trimethyl are to vinyl benzene bromination
Ammonium, chlorocarbon base dimethyl-benzyl amine, ethylenediamine, diethylenetriamine, triethylene tetramine, phthalimide, methacrylic acid
Diformazan ammonia ethyl ester, trimethyl ammonium chloride, trimethyl are to one kind in vinyl benzene ammonium chloride.
7. preparation method according to claim 5, it is characterized in that:The activator is selected from sulfuric acid, acetic acid, hydrochloric acid, sulphur
One kind in acid, trichloroacetic acid, phosphoric acid, isophthalic acid, phthalic acid.
8. preparation method according to claim 5, it is characterized in that:The montmorillonite is selected from sodium-based montmorillonite, Ni-based illiteracy
One kind in de- soil, calcium-base montmorillonite, Sodium/Calcium base montmorillonite, magnesium-based montmorillonite.
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