CN1869114A - Cellulose/montmorillonite nanometer composite material and its preparation method - Google Patents
Cellulose/montmorillonite nanometer composite material and its preparation method Download PDFInfo
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- CN1869114A CN1869114A CN 200610043043 CN200610043043A CN1869114A CN 1869114 A CN1869114 A CN 1869114A CN 200610043043 CN200610043043 CN 200610043043 CN 200610043043 A CN200610043043 A CN 200610043043A CN 1869114 A CN1869114 A CN 1869114A
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Abstract
A nano-class cellulose-montmorillonite composition with high elasticity and high-temp resistance is prepared through intercalating the cellulose between the layers of montmorillonite to make the montmorillonite to bind the cellulose tightly and to be uniformly dispersed in cellulose by nano class.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of compound thermal resistance material, relating in particular to a kind of is that main body interacts with crop stalk fiber and natural montmorillonite, formation have nano composite material---a Mierocrystalline cellulose/Nano composite material of montmorillonite of elasticity and wear resistance preferably.
Background technology
Natural montmorillonite is because its property is widely used as the filler of thermal resistance polymer composites, and filler content is high more within the specific limits, and performance of composites is good more, but the mechanical property of material descends to some extent, and particularly toughness of material can obviously descend.An effective way that improves composite property is that inorganics evenly is filled in the polymkeric substance, can improve its thermal property and mechanical property.
Fiber elastic-material as framework material, makes it keep stable shaped by gluing with suitable fiber.When fiber had the space three-dimensional reticulated structure, the material of preparing had good elasticity.Because gluing fiber elastic-material is permeable, breathe freely, series of advantages such as excellent spring, intensity are reliable more and more widely is applied in the engineering structure in fields such as Aeronautics and Astronautics, traffic, physical culture and personnel protection.
Present Green Chemistry and the Industrial Revolution that brings thereof are risen in the whole world, and the Green Revolution in the heat insulation industry is also coming, and when people increased thermal resistance materials demand amount, performance requriements was also more many-sided.Straw fiber element/Nano composite material of montmorillonite arises at the historic moment, and this material possesses the rigidity and the good workability of organic polymer of inorganics with the organic combination of the characteristic of the two, has the incomparable advantage of traditional material.
Straw is the residual things of seed results back farm crop, the several hundred million tons of annual output, but the utilization ratio of straw is but very low in China, only account for about 5%, most of straw is used as that castoff burning falls or only be used as fuel, has both wasted a large amount of natural resourcess, again environment is polluted, make airborne SO
2And NO
xDeng severe overweight.If can turn waste into wealth, raw material used as elasticity thermal resistance material, will increase utility value, can improve agriculture benefit, reduce the cost of elasticity thermal resistance material, the more important thing is exploitation, can replenish the shortage of the Nonrenewable resources that the mankind face in a large number, human kind sustainable development is had great significance renewable natural resource.
Summary of the invention
The present invention gets purpose and provides a kind of to be that main body interacts with straw fiber and natural montmorillonite, to form a kind of straw fiber element/Nano composite material of montmorillonite of elasticity, wear resistance and thermal resistance preferably that has.
Straw fiber element/Nano composite material of montmorillonite of the present invention is that Mierocrystalline cellulose is evenly inserted in the montmorillonite layer, makes polynite and Mierocrystalline cellulose combine closely and be dispersed in the Mierocrystalline cellulose with nanoscale and get.
Described Mierocrystalline cellulose is the crop branch fiber element, and this crop branch fiber element is with agricultural crop straw high temperature reflux and getting under the acidity condition.
Described polynite is that natural montmorillonite passes through the organically-modified organo montmorillonite that gets.
The preparation method of straw fiber element/Nano composite material of montmorillonite of the present invention comprises following processing step:
1. the preparation of straw fiber element: crop stalk is pulverized, joined in the acidic solution of 60～120 times of straw powder qualities, at 100～120 ℃ of 2～3h that reflux down; Add alkaline neutraliser with the described sour equimolar amount 1～1.5h that refluxes again, suction filtration, with distilled water wash, drying, the straw fiber element; 2. the modification of polynite: natural montmorillonite is placed water, in 40～60 ℃ water bath with thermostatic control, leave standstill behind stirring heating 30～60min, form the polynite aqueous dispersions; The properties-correcting agent of getting 0.3～0.5 times of natural montmorillonite quality places water, the hydrochloric acid that adds 0.5～1 times of natural montmorillonite quality is regulated the protonated solution of formation, and protonated solution dropwise joined in the polynite aqueous dispersions, with vibration of ultrasonic wave after 3～4 hours, suction filtration also washes with water and does not only have bromide anion and chlorion, then under 70～90 ℃, vacuum-drying, grind, sieve organo montmorillonite;
3. intercalation: straw fiber element, organo montmorillonite fully be dissolved in the dispersion medium by 1: 1～1.2 mass ratio stir, again to the fibrolysis agent that wherein adds 0.1～0.15 times of organic polynite quality, under agitation being heated to Mierocrystalline cellulose dissolves fully, suction filtration, typing, washing, after treating that lyosol freezes, promptly at 60～80 ℃ of drying 48～50h.
The 1. described acidic solution of step is that concentration is 60%～65% salpeter solution.
The 1. described alkaline neutraliser of step is a sodium hydroxide.
The 1. described dispersion medium of step is a water.
The 2. described properties-correcting agent of step is Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride.
The 3. described straw fiber solvating agent of step is a zinc chloride.
The structure of the straw fiber/Nano composite material of montmorillonite of the present invention's preparation can be embodied fully by the SEM photo of scanning electron microscope and transmission electron microscope: among Fig. 1, (a) being the montmorillonite layer structure, (b) is that Mierocrystalline cellulose/Nano composite material of montmorillonite amplifies 9.8 * 10
3SEM photo doubly.Can see and evenly coated one deck Mierocrystalline cellulose on the montmorillonite layer from figure (b); Can find out significantly that by figure (b) montmorillonite layer has kept its original laminate structure substantially, Mierocrystalline cellulose has inserted its interlayer, formed regular Mierocrystalline cellulose/montmorillonite material, montmorillonite layer combines with organism closely, has mutual adsorption between them; The laminated structure of polynite has stoped cellulosic gathering, and makes polynite and Mierocrystalline cellulose be uniformly dispersed in reaction process.
The performance of Mierocrystalline cellulose/Nano composite material of montmorillonite of the present invention:
1, elasticity: because the cellulosic existence that has elastomeric property in the matrix material, and Mierocrystalline cellulose and polynite make this nano composite material have elasticity preferably with the nanoscale homodisperse.
Fig. 2 is the influence of cellulose concentration in Mierocrystalline cellulose/montmorillonite composite material of the present invention to real number viscosity (η) and real number modulus (G).As we can see from the figure: real number viscosity (η) and real number modulus (G) increase with the increase of cellulose concentration (C), for real number viscosity (η), at cellulosic concentration C=125mgL
-1There is a weight break point at the place.Real number viscosity (η) is the sign of cellulose solution pure viscosity, is macromolecular chain kinematic viscosity mobile reflection in solution.When cellulosic concentration (C) increase, molecule interchain reactive force increases, and macro manifestations is the increase of real number viscosity.For real number modulus (G), at cellulosic concentration C=500mgL
-1There is a weight break point at the place.Real number modulus (G) is the elastic sign of Mierocrystalline cellulose, and is promptly relevant with the network structure in the solution.As cellulosic concentration C=500mgL
-1The time point that tangles increase comparatively fast with cellulosic concentration C, as C＞500mgL
-1The time point that tangles increase slower with cellulosic concentration C.
2, thermotolerance: owing to have a kind of strong interaction between the interface of Mierocrystalline cellulose and polynite, make the laminated structure of polynite produce obstruct and provide protection to Mierocrystalline cellulose in the nanometer space, limit the reactivity of interlayer cellulosic molecule on the one hand, delayed the carrying out of pyrolysis; Make that on the other hand gas communication is not smooth between the lamella, thereby further suppressed cellulosic thermolysis, therefore, matrix material of the present invention has better heat-resisting.
Fig. 3 is the TG curve of Mierocrystalline cellulose/montmorillonite material (1) and Mierocrystalline cellulose (2).Can find out that by the TG curve maximum heat weightless temperature of solo fibre element is lower than Mierocrystalline cellulose/Nano composite material of montmorillonite.Studies show that, the decomposition temperature of matrix raises, its reason exists the strong molecular interaction between restriction of montmorillonite layer spatial and Mierocrystalline cellulose, polynite simultaneously causes the degree of crosslinking of cellulose molecular chain to increase, thereby improve the thermolysis energy needed, promptly the thermotolerance of material improves.
This shows that Mierocrystalline cellulose/montmorillonite composite material of the present invention combines the advantage of Mierocrystalline cellulose and polynite, has the incomparable advantage of traditional material: elasticity, thermotolerance, improved the workability of matrix material greatly, be with a wide range of applications in fields such as space flight, physical culture and environmental protection.
The present invention prepares the method for Mierocrystalline cellulose/montmorillonite composite material, and technology is simple, easy to operate, the production efficiency height, and cost is low, is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM photo of polynite of the present invention and Mierocrystalline cellulose/montmorillonite material
Fig. 2 is the influence of different concns Mierocrystalline cellulose to real number viscosity (η) and real number modulus (G)
Fig. 3 Mierocrystalline cellulose/montmorillonite material and cellulosic TG curve
Embodiment
The preparation of embodiment 1, Mierocrystalline cellulose/Nano composite material of montmorillonite:
1. the preparation of straw fiber element: corn stalk is pulverized, joined 120 times of straw powder qualities, concentration and be in 60% the salpeter solution, at 120 ℃ of following backflow 2h; The sodium hydroxide backflow 1h that adds the nitric acid equimolar amount again, suction filtration with distilled water wash, drying, gets the straw fiber element;
2. the modification of polynite: natural montmorillonite is placed water, in 40 ℃ water bath with thermostatic control, leave standstill behind stirring heating 30～60min, form the polynite aqueous dispersions; The Trimethyllaurylammonium bromide of getting 0.5 times of natural montmorillonite quality places water, the hydrochloric acid that adds 1 times of natural montmorillonite quality is regulated the protonated solution of formation, and protonated solution dropwise joined in the polynite aqueous dispersions, with vibration of ultrasonic wave after 3～4 hours, suction filtration also washes with water and does not only have bromide anion and chlorion, then under 70 ℃, vacuum-drying, grind, sieve organo montmorillonite;
3. intercalation: with straw fiber element, organo montmorillonite by abundant soluble in water the stirring of 1: 1 mass ratio, again to the zinc chloride that wherein adds 0.1 times of organic polynite quality, under agitation being heated to Mierocrystalline cellulose dissolves fully, suction filtration, typing, washing, after treating that lyosol freezes, promptly at 70 ℃ of drying 48～50h.
The preparation of embodiment 2, Mierocrystalline cellulose/Nano composite material of montmorillonite:
1. the preparation of straw fiber element: wheat straw is pulverized, joined 90 times of straw powder qualities, concentration and be in 62% the salpeter solution, at 110 ℃ of following backflow 3h; The sodium hydroxide backflow 1.5h that adds the nitric acid equimolar amount again, suction filtration with distilled water wash, drying, gets the straw fiber element;
2. the modification of polynite: natural montmorillonite is placed water, in 50 ℃ water bath with thermostatic control, leave standstill behind stirring heating 30～60min, form the polynite aqueous dispersions; The cetyl trimethylammonium bromide of getting 0.3 times of natural montmorillonite quality places water, the hydrochloric acid that adds 0.8 times of natural montmorillonite quality is regulated the protonated solution of formation, and protonated solution dropwise joined in the polynite aqueous dispersions, with vibration of ultrasonic wave after 3～4 hours, suction filtration also washes with water and does not only have bromide anion and chlorion, then under 90 ℃, vacuum-drying, grind, sieve organo montmorillonite;
3. intercalation: with straw fiber element, organo montmorillonite by abundant soluble in water the stirring of 1: 1.15 mass ratio, again to the zinc chloride that wherein adds 0.12 times of organic polynite quality, under agitation being heated to Mierocrystalline cellulose dissolves fully, suction filtration, typing, washing, after treating that lyosol freezes, promptly at 60 ℃ of drying 48～50h.
The preparation of embodiment 3, Mierocrystalline cellulose/Nano composite material of montmorillonite:
1. the preparation of straw fiber element: corn stalk is pulverized, joined 60 times of straw powder qualities, concentration and be in 65% the salpeter solution, at 100 ℃ of following backflow 2.5h; The sodium hydroxide backflow 1.3h that adds the nitric acid equimolar amount again, suction filtration with distilled water wash, drying, gets the straw fiber element;
2. the modification of polynite: natural montmorillonite is placed water, in 60 ℃ water bath with thermostatic control, leave standstill behind stirring heating 30～60min, form the polynite aqueous dispersions; The octadecyl trimethyl ammonium chloride of getting 0.4 times of natural montmorillonite quality places water, the hydrochloric acid that adds 1 times of natural montmorillonite quality is regulated the protonated solution of formation, and protonated solution dropwise joined in the polynite aqueous dispersions, with vibration of ultrasonic wave after 3～4 hours, suction filtration also washes with water and does not only have bromide anion and chlorion, then under 80 ℃, vacuum-drying, grind, sieve organo montmorillonite;
3. intercalation: with straw fiber element, organo montmorillonite by abundant soluble in water the stirring of 1: 1.2 mass ratio, again to the zinc chloride that wherein adds 0.15 times of organic polynite quality, under agitation being heated to Mierocrystalline cellulose dissolves fully, suction filtration, typing, washing, after treating that lyosol freezes, promptly at 80 ℃ of drying 48～50h.
Claims (10)
1, a kind of Mierocrystalline cellulose/Nano composite material of montmorillonite is that Mierocrystalline cellulose is evenly inserted in the montmorillonite layer, makes polynite and Mierocrystalline cellulose combine closely and be dispersed in the Mierocrystalline cellulose with nanoscale and get.
2, Mierocrystalline cellulose/Nano composite material of montmorillonite as claimed in claim 1 is characterized in that: described polynite is that natural montmorillonite passes through the organo montmorillonite that organic modifiers gets.
3, Mierocrystalline cellulose/Nano composite material of montmorillonite as claimed in claim 1 is characterized in that: described Mierocrystalline cellulose is the crop branch fiber element.
4, Mierocrystalline cellulose/Nano composite material of montmorillonite as claimed in claim 3 is characterized in that: described crop branch fiber element is with agricultural crop straw high temperature reflux and getting under the acidity condition.
5, a kind of preparation method of straw fiber element/Nano composite material of montmorillonite comprises following processing step:
1. the preparation of straw fiber element: crop stalk is pulverized, joined in the acidic solution of 60～120 times of straw powder qualities, at 100～120 ℃ of 2～3h that reflux down; Add alkaline neutraliser with the described sour equimolar amount 1～1.5h that refluxes again, suction filtration, with distilled water wash, drying, the straw fiber element;
2. the modification of polynite: natural montmorillonite is placed water, in 40～60 ℃ water bath with thermostatic control, leave standstill behind stirring heating 30～60min, form the polynite aqueous dispersions; The properties-correcting agent of getting 0.3～0.5 times of natural montmorillonite quality places water, the hydrochloric acid that adds 0.5～1 times of natural montmorillonite quality is regulated the protonated solution of formation, and protonated solution dropwise joined in the polynite aqueous dispersions, with vibration of ultrasonic wave after 3～4 hours, suction filtration also washes with water and does not only have bromide anion and chlorion, then under 70～90 ℃, vacuum-drying, grind, sieve organo montmorillonite;
3. intercalation: straw fiber element, organo montmorillonite fully be dissolved in the dispersion medium by 1: 1～1.2 mass ratio stir, again to the fibrolysis agent that wherein adds 0.1～0.15 times of organic polynite quality, under agitation being heated to Mierocrystalline cellulose dissolves fully, suction filtration, typing, washing, after treating that lyosol freezes, promptly at 60～80 ℃ of drying 48～50h.
6, as the preparation method of straw fiber element/Nano composite material of montmorillonite as described in the claim 5, it is characterized in that: the 1. described acidic solution of step is that concentration is 60%～65% salpeter solution.
7, as the preparation method of straw fiber element/Nano composite material of montmorillonite as described in the claim 5, it is characterized in that: the 1. described alkaline neutraliser of step is a sodium hydroxide.
8, as the preparation method of straw fiber element/Nano composite material of montmorillonite as described in the claim 5, it is characterized in that: the 2. described properties-correcting agent of step is Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride.
9, as the preparation method of straw fiber element/Nano composite material of montmorillonite as described in the claim 5, it is characterized in that: the 3. described dispersion medium of step is a water.
10, as the preparation method of straw fiber element/Nano composite material of montmorillonite as described in the claim 5, it is characterized in that: the 3. described straw fiber solvating agent of step is a zinc chloride.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416312A (en) * | 2011-10-18 | 2012-04-18 | 内蒙古农业大学 | Dye wastewater absorbent prepared by compounding lignocellulose and calcium-based montmorillonite |
| CN103613790A (en) * | 2013-11-19 | 2014-03-05 | 齐鲁工业大学 | Preparation method of cellulose-based composite material |
| CN105694110A (en) * | 2016-01-26 | 2016-06-22 | 中南林业科技大学 | Aperture-adjustable cellulose and montmorillonite nano-composite carrier material and preparation method thereof |
| CN106634441A (en) * | 2016-12-28 | 2017-05-10 | 安徽燎原电器设备制造有限公司 | Double-ingredient waterborne epoxy paint for distribution cabinet case |
| CN106758500A (en) * | 2016-12-20 | 2017-05-31 | 齐鲁工业大学 | A kind of method of the modified papermaking filler of utilization cationic cellulose derivative |
| CN110886025A (en) * | 2019-12-17 | 2020-03-17 | 上海里奥纤维企业发展有限公司 | Solvent method high wet modulus protein fiber and preparation method thereof |
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2006
- 2006-06-24 CN CN 200610043043 patent/CN1869114A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416312A (en) * | 2011-10-18 | 2012-04-18 | 内蒙古农业大学 | Dye wastewater absorbent prepared by compounding lignocellulose and calcium-based montmorillonite |
| CN103613790A (en) * | 2013-11-19 | 2014-03-05 | 齐鲁工业大学 | Preparation method of cellulose-based composite material |
| CN103613790B (en) * | 2013-11-19 | 2016-04-13 | 齐鲁工业大学 | A kind of preparation method of cellulose base matrix material |
| CN105694110A (en) * | 2016-01-26 | 2016-06-22 | 中南林业科技大学 | Aperture-adjustable cellulose and montmorillonite nano-composite carrier material and preparation method thereof |
| CN105694110B (en) * | 2016-01-26 | 2018-08-14 | 中南林业科技大学 | A kind of adjustable cellulose in aperture and montmorillonite-based nano composite carrier and preparation method thereof |
| CN106758500A (en) * | 2016-12-20 | 2017-05-31 | 齐鲁工业大学 | A kind of method of the modified papermaking filler of utilization cationic cellulose derivative |
| CN106634441A (en) * | 2016-12-28 | 2017-05-10 | 安徽燎原电器设备制造有限公司 | Double-ingredient waterborne epoxy paint for distribution cabinet case |
| CN110886025A (en) * | 2019-12-17 | 2020-03-17 | 上海里奥纤维企业发展有限公司 | Solvent method high wet modulus protein fiber and preparation method thereof |
| CN110886025B (en) * | 2019-12-17 | 2022-07-05 | 上海里奥纤维企业发展有限公司 | Solvent method high wet modulus protein fiber and preparation method thereof |
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