CN103265638A - Method for preparing cellulose nano whisker organic-inorganic heat resisting hybrid material - Google Patents
Method for preparing cellulose nano whisker organic-inorganic heat resisting hybrid material Download PDFInfo
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- CN103265638A CN103265638A CN2013102359353A CN201310235935A CN103265638A CN 103265638 A CN103265638 A CN 103265638A CN 2013102359353 A CN2013102359353 A CN 2013102359353A CN 201310235935 A CN201310235935 A CN 201310235935A CN 103265638 A CN103265638 A CN 103265638A
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Abstract
The invention discloses a method for preparing a cellulose nano whisker organic-inorganic heat resisting hybrid material. The preparation method comprises the following steps of carrying out surface treatment on cellulose nano whiskers by a cross-linking agent, so as to form epoxidized cellulose nano whiskers, then enabling the epoxidized cellulose nano whiskers and polyhedral oligomeric silsesquioxanes (POSS) to react so as to prepare the cellulose nano whisker organic inorganic heat resisting hybrid material. The preparation method is applicable to preparation of organic inorganic heat resisting hybrid materials of cellulose particles (such as cellulose microcrystal, cellulose microfiber and cellulose nanofiber) prepared by various natural plants, the POSS nano particles used in the method have good dispersibility, an epoxy group and-NH2 contained in the POSS have good reactivity and are beneficial to reaction of POSS grafting cellulose nano whiskers, the thermal property of the prepared hybrid material is improved obviously, and the problem of poor heat resistance of the existing cellulose nano whiskers used as a reinforcing material is solved.
Description
Technical field
The invention belongs to the hybrid material preparing technical field, particularly the heat-stable hybridized preparation methods of a kind of Mierocrystalline cellulose nano whisker organic-inorganic.
Background technology
In order to tackle world today's energy, resource, problems such as environment, development is green, environmental protection, renewable, degradable material has become much-talked-about topic.Mierocrystalline cellulose is as the abundantest natural polymer on a kind of earth, and it just has recyclable regenerative, degradable, good biocompatibility, high specific strength, advantage such as cheap, widespread use and food, medicine, fields such as material.
The Mierocrystalline cellulose nano whisker be with natural plant fibre by acid hydrolysis, means such as enzymic hydrolysis obtain has high length-diameter ratio, high-specific surface area, the vegetable fibre of high strength (theoretical value 250Gpa).But because cellulosic natural characteristic, its thermotolerance is not high, as high-intensity strongthener strengthen polymer resin matrix the time tend to reduce the resistance toheat of resin.Simultaneously, the Mierocrystalline cellulose nano whisker is in preparation process, because the change of acid hydrolysis and structure and morphology, its resistance toheat also further decreases.Drop to about 145 ℃ for about 300 ℃ from cellulose crystallite (particle diameter is about 10um) heat resisting temperature as its thermotolerance.Therefore, the thermotolerance that how to improve the Mierocrystalline cellulose nano whisker will be a major issue that the assistant officer is to be solved.
Summary of the invention
The objective of the invention is provides a kind of Mierocrystalline cellulose nano whisker organic-inorganic heat-stable hybridized preparation methods in order to solve the not good problem of Mierocrystalline cellulose nano whisker thermotolerance.
The purpose of present method is in order to solve the not good problem of Mierocrystalline cellulose nano whisker thermotolerance, to change its stable on heating method and propose a kind of inorganic nano-particle POSS hydridization by Mierocrystalline cellulose nano whisker and excellent heat resistance
Thinking of the present invention:
At first adopt linking agent that Mierocrystalline cellulose nano whisker surface is handled, form epoxidation Mierocrystalline cellulose nano whisker, with polyhedron oligomeric silsesquioxanes (POSS) reaction of epoxidation Mierocrystalline cellulose nano whisker and excellent heat resistance, be prepared into the heat-stable hybridized material of Mierocrystalline cellulose nano whisker organic-inorganic again.
Concrete steps of the present invention are:
(1) the Mierocrystalline cellulose nano whisker is joined in the NaOH solution that concentration is 1 mol, Mierocrystalline cellulose nano whisker and concentration are that the solid-to-liquid ratio of the NaOH solution of 1 mol is 1 gram: 335 ~ 345 milliliters, used the gap ultra-sonic dispersion 30 ~ 60 minutes, ultrasound intensity is 400 watts, and the timed interval is 6 minutes.
(2) solution after step (1) is disperseed is moved in three mouthfuls of reaction vessels, magnetic agitation also is warming up to 58 ~ 62 ℃, slowly add epoxy chloropropane after 30 ~ 60 minutes, the solid-to-liquid ratio of Mierocrystalline cellulose nano whisker and epoxy chloropropane is 1 gram: 5 ~ 8 milliliters, insulation reaction 2 ~ 3 times of dilute with waters after 2 hours, remove alkali and unreacted epoxy chloropropane in the solution with dialysis tubing dialysis, last lyophilize namely makes epoxidation Mierocrystalline cellulose nano whisker.
(3) the epoxidation Mierocrystalline cellulose nano whisker that step (2) is made is distributed in the distilled water, and the solid-to-liquid ratio of epoxidation Mierocrystalline cellulose nano whisker and distilled water is 1 gram: 995 ~ 1005 milliliters, make epoxidation Mierocrystalline cellulose nano whisker dispersion liquid.
(4) take by weighing POSS-NH
2Be the octa-aminopropyl oligomeric silsesquioxanes, its quality be the epoxidation Mierocrystalline cellulose nano whisker that makes of step (2) quality 9.5 ~ 10.5%, be added in the distilled water of 100 times of quality, magnetic agitation dissolving and intensification degree to 65 ~ 75 ℃ make POSS-NH
2Solution.
(5) POSS-NH that step (4) is made
2Solution slowly is added drop-wise in the epoxidation Mierocrystalline cellulose nano whisker dispersion liquid that step (3) makes, 65 ~ 75 ℃ of insulations 3 hours, with the reaction solution lyophilize, more dried product is disperseed centrifuge washing with anhydrous methanol, ultra-sonic dispersion 20 ~ 60 minutes dissolves unreacted POSS-NH
2It is the octa-aminopropyl oligomeric silsesquioxanes, centrifugation then, repeat above-mentioned dispersion centrifuge washing process 3 ~ 4 times, product after disperseing centrifuge washing is disperseed with deionized water, product after disperseing centrifuge washing and the solid-to-liquid ratio of deionized water are 1 gram: 98 ~ 102 milliliters, used the gap ultra-sonic dispersion 30 ~ 60 minutes, ultrasound intensity is 400 watts, the timed interval is 6 minutes, centrifugal removal lower sediment is got the dry heat-stable hybridized material of Mierocrystalline cellulose nano whisker organic-inorganic that namely makes of the turbid liquid cooling freeze-drying in upper strata again.
Described Mierocrystalline cellulose nano whisker is to extract the Mierocrystalline cellulose nano whisker that hydrolysis makes from timber, bamboo, paper pulp, cotton or sisal hemp, and its diameter is 3 ~ 5 nanometers, and length is 10 ~ 100 nanometers, is the nano-fiber material of acicular structure.
Described octa-aminopropyl oligomeric silsesquioxanes is to serve as nuclear and eight organic inorganic hybridization small molecules that drift angle is organo-functional group with the octahedron that Si-O-Si forms, and the size of molecule itself is 2 ~ 4 nanometers.
The purity of described chemical reagent and raw material is analytical pure and above purity.
The advantage of the inventive method:
(1) the inventive method is applicable to the preparation of the heat-stable hybridized material of organic-inorganic of the cellulose family particle (comprise cellulose crystallite, Mierocrystalline cellulose fento, cellulose nano-fibrous etc.) of various natural phant preparation.
(2) the POSS nanoparticle that uses in the inventive method has good dispersiveness, and be with-NH
2Has good reactive behavior with epoxide group, be conducive to the reaction of POSS grafted cellulose nano whisker, compare with pure Mierocrystalline cellulose nano whisker, the thermal characteristics of hybrid material has raising significantly, the not good problem of thermotolerance when having solved present Mierocrystalline cellulose nano whisker as strongthener.
Description of drawings
Fig. 1 is the thermogravimetic analysis (TGA) curve of the heat-stable hybridized material of organic-inorganic (representing with SCNW/POSS) of the plain nano whisker of POSS grafting sisal fibers of the plain nano whisker (representing with SCNW) of the sisal fibers that uses in the embodiment of the invention, octa-aminopropyl oligomeric silsesquioxanes (representing with POSS) and preparation.
Fig. 2 is differential thermal gravimetric analysis (DTG) curve of the heat-stable hybridized material of organic-inorganic (representing with SCNW/POSS) of the plain nano whisker of POSS grafting sisal fibers of the plain nano whisker (representing with SCNW) of the sisal fibers that uses in the embodiment of the invention, octa-aminopropyl oligomeric silsesquioxanes (representing with POSS) and preparation.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples, employed chemical reagent and raw material are analytical pure in following examples.
Embodiment:
(1) the plain nano whisker of 1 gram sisal fibers is joined in the NaOH solution that 340 ml concns are 1 mol, used the gap ultra-sonic dispersion 45 minutes, ultrasound intensity is 400 watts, and the timed interval is 6 minutes.
(2) in the there-necked flask with 500 milliliters of the immigrations of the solution after step (1) is disperseed, magnetic agitation also is warming up to 60 ℃, slowly add 7 milliliters of epoxy chloropropane after 45 minutes, insulation reaction 3 times of dilute with waters after 2 hours, remove alkali and unreacted epoxy chloropropane in the solution with dialysis tubing dialysis, last lyophilize namely makes the plain nano whisker of epoxidation sisal fibers.
(3) the plain nano whisker of the epoxidation sisal fibers that step (2) is made is distributed in 1000 ml distilled waters, makes the plain nano whisker dispersion liquid of epoxidation sisal fibers.
(4) take by weighing POSS-NH
2Be the octa-aminopropyl oligomeric silsesquioxanes, its quality be the epoxidation Mierocrystalline cellulose nano whisker that makes of step (2) quality 10%, be added in the distilled water of 100 times of quality, magnetic agitation dissolving and intensification degree to 70 ℃ make POSS-NH
2Solution.
(5) POSS-NH that step (4) is made
2Solution slowly is added drop-wise in the epoxidation Mierocrystalline cellulose nano whisker dispersion liquid that step (3) makes, 70 ℃ of insulations 3 hours, with the reaction solution lyophilize, more dried product is disperseed centrifuge washing with anhydrous methanol, ultra-sonic dispersion 40 minutes dissolves unreacted POSS-NH
2It is the octa-aminopropyl oligomeric silsesquioxanes, centrifugation then, repeat above-mentioned dispersion centrifuge washing process 4 times, product after disperseing centrifuge washing is disperseed with 100 ml deionized water, gap ultra-sonic dispersion 45 minutes, ultrasound intensity are 400 watts, and the timed interval is 6 minutes, centrifugal removal lower sediment is got the dry heat-stable hybridized material of organic-inorganic that namely makes the plain nano whisker of POSS grafting sisal fibers of the turbid liquid cooling freeze-drying in upper strata again.
The heat decomposition temperature of the heat-stable hybridized material of organic-inorganic of the plain nano whisker of hot analytical results demonstration POSS grafting sisal fibers has improved 132 ℃ than the heat resisting temperature of the plain nano whisker of sisal fibers, its temperature of initial decomposition reaches 285.8 ℃ (the thermogravimetric analysis graphic representation is seen accompanying drawing 1, and the DTG curve is seen accompanying drawing 2).
Claims (1)
1. heat-stable hybridized preparation methods of Mierocrystalline cellulose nano whisker organic-inorganic is characterized in that concrete steps are:
(1) the Mierocrystalline cellulose nano whisker is joined in the NaOH solution that concentration is 1 mol, Mierocrystalline cellulose nano whisker and concentration are that the solid-to-liquid ratio of the NaOH solution of 1 mol is 1 gram: 335 ~ 345 milliliters, used the gap ultra-sonic dispersion 30 ~ 60 minutes, ultrasound intensity is 400 watts, and the timed interval is 6 minutes;
(2) solution after step (1) is disperseed is moved in three mouthfuls of reaction vessels, magnetic agitation also is warming up to 58 ~ 62 ℃, slowly add epoxy chloropropane after 30 ~ 60 minutes, the solid-to-liquid ratio of Mierocrystalline cellulose nano whisker and epoxy chloropropane is 1 gram: 5 ~ 8 milliliters, insulation reaction 2 ~ 3 times of dilute with waters after 2 hours, remove alkali and unreacted epoxy chloropropane in the solution with dialysis tubing dialysis, last lyophilize namely makes epoxidation Mierocrystalline cellulose nano whisker;
(3) the epoxidation Mierocrystalline cellulose nano whisker that step (2) is made is distributed in the distilled water, and the solid-to-liquid ratio of epoxidation Mierocrystalline cellulose nano whisker and distilled water is 1 gram: 995 ~ 1005 milliliters, make epoxidation Mierocrystalline cellulose nano whisker dispersion liquid;
(4) take by weighing POSS-NH
2Be the octa-aminopropyl oligomeric silsesquioxanes, its quality be the epoxidation Mierocrystalline cellulose nano whisker that makes of step (2) quality 9.5 ~ 10.5%, be added in the distilled water of 100 times of quality, magnetic agitation dissolving and intensification degree to 65 ~ 75 ℃ make POSS-NH
2Solution;
(5) POSS-NH that step (4) is made
2Solution slowly is added drop-wise in the epoxidation Mierocrystalline cellulose nano whisker dispersion liquid that step (3) makes, 65 ~ 75 ℃ of insulations 3 hours, with the reaction solution lyophilize, more dried product is disperseed centrifuge washing with anhydrous methanol, ultra-sonic dispersion 20 ~ 60 minutes dissolves unreacted POSS-NH
2It is the octa-aminopropyl oligomeric silsesquioxanes, centrifugation then, repeat above-mentioned dispersion centrifuge washing process 3 ~ 4 times, product after disperseing centrifuge washing is disperseed with deionized water, product after disperseing centrifuge washing and the solid-to-liquid ratio of deionized water are 1 gram: 98 ~ 102 milliliters, used the gap ultra-sonic dispersion 30 ~ 60 minutes, ultrasound intensity is 400 watts, the timed interval is 6 minutes, centrifugal removal lower sediment is got the dry heat-stable hybridized material of Mierocrystalline cellulose nano whisker organic-inorganic that namely makes of the turbid liquid cooling freeze-drying in upper strata again;
Described Mierocrystalline cellulose nano whisker is to extract the Mierocrystalline cellulose nano whisker that hydrolysis makes from timber, bamboo, paper pulp, cotton or sisal hemp, and its diameter is 3 ~ 5 nanometers, and length is 10 ~ 100 nanometers, is the nano-fiber material of acicular structure;
Described octa-aminopropyl oligomeric silsesquioxanes is to serve as nuclear and eight organic inorganic hybridization small molecules that drift angle is organo-functional group with the octahedron that Si-O-Si forms, and the size of molecule itself is 2 ~ 4 nanometers;
The purity of described chemical reagent and raw material is analytical pure and above purity.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601917A (en) * | 2013-09-11 | 2014-02-26 | 郑州轻工业学院 | Water-soluble organosilicon/cellulose ether nanometer hybrid material, preparation method thereof and applications thereof |
| CN108276605A (en) * | 2018-01-26 | 2018-07-13 | 青岛科技大学 | A method of preparing inorganic crystal whisker/POSS hybrid materials using sulfydryl-alkene click-reaction |
| CN109610035A (en) * | 2018-11-26 | 2019-04-12 | 福建省银河服饰有限公司 | Cage type polysilsesquioxane and nanometer Tai Ji stone are total to modified polyester fiber and preparation method thereof and textile |
| CN113956543A (en) * | 2021-12-15 | 2022-01-21 | 兴宇汽车零部件股份有限公司 | Hyperbranched ionic liquid/CNFs hybrid particle, microporous foaming flame retardant TPV and preparation method thereof |
| CN115403674A (en) * | 2022-05-12 | 2022-11-29 | 盐城工学院 | Biomass-based enhanced flame retardant and preparation method and application thereof |
| WO2023234072A1 (en) * | 2022-05-30 | 2023-12-07 | 日信化学工業株式会社 | Cellulose-siloxane composite particles, method for producing same, and cosmetic |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601917A (en) * | 2013-09-11 | 2014-02-26 | 郑州轻工业学院 | Water-soluble organosilicon/cellulose ether nanometer hybrid material, preparation method thereof and applications thereof |
| CN103601917B (en) * | 2013-09-11 | 2016-04-27 | 郑州轻工业学院 | Water-soluble organic silicon ether of cellulose nano-hybrid material and preparation method thereof and application |
| CN108276605A (en) * | 2018-01-26 | 2018-07-13 | 青岛科技大学 | A method of preparing inorganic crystal whisker/POSS hybrid materials using sulfydryl-alkene click-reaction |
| CN108276605B (en) * | 2018-01-26 | 2020-02-18 | 青岛科技大学 | Method for preparing inorganic whisker/POSS hybrid material by utilizing sulfydryl-alkene click reaction |
| CN109610035A (en) * | 2018-11-26 | 2019-04-12 | 福建省银河服饰有限公司 | Cage type polysilsesquioxane and nanometer Tai Ji stone are total to modified polyester fiber and preparation method thereof and textile |
| CN109610035B (en) * | 2018-11-26 | 2021-09-03 | 福建省银河服饰有限公司 | Cage polysilsesquioxane and nano taiji stone co-modified polyester fiber, preparation method thereof and textile |
| CN113956543A (en) * | 2021-12-15 | 2022-01-21 | 兴宇汽车零部件股份有限公司 | Hyperbranched ionic liquid/CNFs hybrid particle, microporous foaming flame retardant TPV and preparation method thereof |
| CN113956543B (en) * | 2021-12-15 | 2022-11-01 | 兴宇汽车零部件股份有限公司 | Hyperbranched ionic liquid/CNFs hybrid particle, microporous foaming flame retardant TPV and preparation method thereof |
| CN115403674A (en) * | 2022-05-12 | 2022-11-29 | 盐城工学院 | Biomass-based enhanced flame retardant and preparation method and application thereof |
| CN115403674B (en) * | 2022-05-12 | 2023-11-21 | 盐城工学院 | Biomass-based enhanced flame retardant, and preparation method and application thereof |
| WO2023234072A1 (en) * | 2022-05-30 | 2023-12-07 | 日信化学工業株式会社 | Cellulose-siloxane composite particles, method for producing same, and cosmetic |
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Application publication date: 20130828 |