CN109880056A - A kind of three-phase cross linking membrane and preparation method thereof of graphene oxide-polyurethane modified cellulose - Google Patents
A kind of three-phase cross linking membrane and preparation method thereof of graphene oxide-polyurethane modified cellulose Download PDFInfo
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- CN109880056A CN109880056A CN201910181460.1A CN201910181460A CN109880056A CN 109880056 A CN109880056 A CN 109880056A CN 201910181460 A CN201910181460 A CN 201910181460A CN 109880056 A CN109880056 A CN 109880056A
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Abstract
The invention discloses a kind of graphene oxide-polyurethane modified cellulose three-phase cross linking membranes and preparation method thereof.Compound cellulose film of the present invention is first to crosslink the isocyanate group in 6- methylene diisocyanate with graphene oxide as grafting point to react, it crosslinks and reacts with the cellulose for being dissolved in ionic liquid [Amim] Cl/DMF in the mixed solvent again, then by solvent displacement, drying and forming-film, graphene oxide-polyurethane modified cellulose three-phase cross linking membrane is prepared.There is good heat resistance, chemical solvent resistance and mechanical property using composite membrane prepared by the present invention, furthermore there is low cost, advantages of environment protection as raw material using reproducible cellulose.
Description
Technical field
The present invention relates to cellulose modified Material Fields, and in particular to a kind of graphene oxide-polyurethane modified cellulose
Three-phase cross linking membrane and preparation method thereof.
Background technique
Cellulose is most abundant, reproducible natural polymer on the earth, have it is cheap, degradable, environmentally friendly and
The features such as biocompatibility, therefore research and research and development to cellulose are all attached great importance in countries in the world.The structure of cellulosic molecule
Formula is (C6H10O5)nIt is the linear molecule being formed by connecting by many D- glucopyranoses with β -1-4 glycosidic bond, each glucose unit
In have 3 polar hydroxyl groups.Since the higher crystallinity of cellulose itself and the strong hydrogen bond of molecule interchain and intramolecule are made
With so that cellulose does not dissolve in Conventional solvents, this largely constrains the application of cellulose.And due to regenerated fiber
The limitation of plain self structure greatly limits so that cellulose membrane poor mechanical property, penetrability are big, meet the problems such as fire easily burns
Its application in fields such as life, industry.Therefore attached desired by people in order to solve the problems, such as cellulose dissolution and receive
Additivity energy, it is necessary to be modified after carrying out dissolution regeneration to cellulosic structure.It is bigger to be run through the modified cellulose scope of application,
Performance makes moderate progress.
Graphene oxide is the two-dimensional layer material with abundant oxygen-containing functional group, its structure and graphene substantially phase
Seemingly, but it is different be that oxygen-containing functional group and hydroxyl are located on the basal plane of graphene, and carboxyl and carbonyl are mainly connected to graphite
The edge of alkene, these oxygen-containing functional groups assign graphene oxide certain hydrophily.And long-chain fat hydrocarbon, transition metal from
Son, hydrophilic molecule and polymer etc. are easy to be inserted into interlayer by the effects of interlayer hydrogen bond, ionic bond and covalent bond, form interlayer
Compound, and then effectively promote mechanical property, chemical property, crystal property of polymer composites etc..
Polyurethane is that one kind made of isocyanates and polyol reaction has carbamic acid segment constitutional repeating unit
Polymer.As thin polymer film application field is increasingly extensive, traditional polyolefin film cannot fully meet market and need
It asks, polyurethane film comes into being.Polyurethane is a kind of high molecular material, since it is with high-strength, high-elastic, heat-resisting, wear-resisting, resistance to
The characteristics such as chemicals, it is considered to be the combination of rubber and plastics excellent properties, in recent years UF membrane field such as pervaporation,
Gaseous jet simulation, ultra-filtration and separation etc. application, is expected to become a kind of novel membrane material.
The present invention using phase inversion method using the isocyanate group in 6- methylene diisocyanate as graft point, respectively with
Graphene oxide, cellulose be crosslinked compound and multiple by the cellulose that three-phase crosslinking is prepared in eluting solvent drying
Close film.The composite membrane has green light weight, good mechanical strength and preferable thermal stability etc., and this give cellulose fibers
Specific performance is tieed up, to expand the application range of cellulose.
Summary of the invention
The purpose of the present invention is to provide one kind to have green light weight, excellent mechanical performances, heat resistance and chemical stability
Cellulose base composite membrane, and provide a kind of method for preparing above-mentioned composite membrane.
To achieve the goals above, the cellulose composite membrane prepared by the present invention is with a thickness of 10 μm~500 μm, porosity
30%~80%, composition includes cellulose, 6- methylene diisocyanate (HDI) and graphene oxide (GO).With compound
Based on cellulosic separator gross mass, content of cellulose be 75%~85%, 6- methylene diisocyanate content be 5%~
25%, graphene oxide content is 0.3%~5%.
A kind of preparation method of the three-phase cross linking membrane of graphene oxide-polyurethane modified cellulose it is as follows including following
Step:
1) by graphene oxide, by 20~30min of ultrasonic treatment, to be dispersed in N,N-dimethylformamide (DMF) molten
In liquid, under inert gas protection, 6- methylene diisocyanate is added thereto uniformly mixed, adds catalyst-two
Dibutyl tin laurate, is warming up to 50 DEG C~100 DEG C 2~12h of reaction, and catalyst amount is 1%~5%；
2) lignocellulosic material of processing to over dry is dissolved completely in ionic liquid [Amim] Cl/DMF and fibre is made
Plain casting solution is tieed up, solution temperature is 60 DEG C~100 DEG C；
3) obtained graphene oxide and 6- methylene diisocyanate cross-linking products are added in cellulose casting solution
Sufficiently reaction is added catalyst-dibutyl tin dilaurate, is warming up to 85 DEG C~100 DEG C 0.5~2h of reaction, catalyst amount
It is 1%~5%；
4) mixing casting solution scrapes rapidly the film of uniform thickness with scraper after standing and defoaming, and film is immersed and is steamed
It in distilled water after eluting solvent, is dried in room temperature to 100 DEG C, finally obtained cellulose composite diaphragm.
Film thickness: using the thickness of micrometer (0.01 millimeter of precision) test composite membrane, appointing and take 5 point measurements on sample,
And it is averaged.
Cellulose pattern: the surface of composite membrane and the form in cross section are observed with scanning electron microscope.
Infrared spectroscopy: the characteristic peak of composite material and composite membrane is observed using infrared spectrometer.
Thermogravimetric analysis: the thermostabilization after observation adds polyurethane and graphene oxide before modified changes.
Tensile strength: the tensile strength and elongation of composite membrane are tested using universal testing machine.
Compared with prior art, the beneficial effects of the present invention are embodied in the following aspects:
The rich material resources of the cellulose composite membrane of one, preparation, cheap environmental protection, source is easy to get, preparation process is simple, behaviour
Facilitate.
Oxide of the two, graphene oxides as graphene, structure is similar, and two-dimentional primary surface connects various oxidation functions
Group.Make it as nano material, there is small-size effect, bigger serface and strong―binding interface ability.Pass through composite polyurethane
Graft modification prepares modified material, and can play the effect for increasing paving, enhancing to film as reinforcing agent, makes the comprehensive performance of composite membrane
It greatly improves.
Three, polyurethane have the characteristics such as high-elastic, high-strength, wear-resisting, heat-resisting, chemicals-resistant, can be again by cheap and easy to get
Production-goods source-timber completely or partially substitutes synthesizing polyether glycol, prepares environmental protection, biodegradable polyurethane-fiber material
Material.Under certain reaction condition, 6- methylene diisocyanate and fibrin reaction utilize the isocyanates in isocyanates
A large amount of hydroxyl (- OH) generates degradable polyurethane-cellulose membrane by graft copolymerization in base (- NCO) and cellulose, so that multiple
Closing film has better mechanical property and thermal stability.
Four, are grafting point using the isocyanate group at both ends in 6- methylene diisocyanate, by adjusting suitably matching
Than, respectively with cellulose, graphene oxide cross-linking reaction, thus generate have rock-steady structure three-phase crosslinked composite membrane so that
The mechanical property of composite membrane is improved significantly.
Detailed description of the invention
Fig. 1 is FT-IR spectrogram
GO in figure, represents graphene oxide；GO-PU in figure represents graphene oxide/compound polyurethane material；Figure
Middle Cellulose, represents cellulose membrane；C-PU in figure represents polyurethane/cellulose membrane.
Fig. 2 is heat decomposition curve figure
A in figure represents graphene oxide/cellulose membrane；C in figure represents polyurethane/cellulose membrane；B in figure, generation
Polyurethane/cellulose membrane of table graphene oxide modification.
Specific embodiment
Below with reference to specific example, the present invention will be further described, but the present invention does not limit to following embodiment.
Embodiment 1
0.1g graphene oxide is dispersed in 50ml DMF solution by being ultrasonically treated 30min, in the guarantor of nitrogen
Under shield, the 6- methylene diisocyanate of 1.4g is added thereto uniformly mixed, and 0.03g dibutyl tin dilaurate is added
React 1.5h.20g [Amim] Cl and DMF (2:1) in the mixed solvent is added in the abundant dry fiber element of 1.0g, in 50 DEG C of water-baths
Stirring takes 0.16g graphene oxide-urethane crosslinks product to be added in cellulose casting solution, and 5d is added to being completely dissolved
Catalyst-dibutyl tin dilaurate is allowed to sufficiently react, and is warming up to 100 DEG C of reaction 2h.After casting solution standing and defoaming being mixed
It is poured on clean glass plate, scrapes the film for producing 50 μm of uniform thickness rapidly with scraper.Glass plate is immersed in distilled water again
Hygrometric state compound cellulose film is taken out after eluting solvent, the cellulose membrane of three-phase crosslinking is obtained after natural air drying.
Embodiment 2
0.15g graphene oxide is dispersed in 100ml DMF solution by being ultrasonically treated 50min, in nitrogen
Under protection, the 6- methylene diisocyanate of 2g is added thereto uniformly mixed, and 0.03g dibutyl tin dilaurate is added
React 3h.25g [Amim] Cl and DMF (6:4) in the mixed solvent is added in the abundant dry fiber element of 1.0g, is stirred in 60 DEG C of water-baths
It mixes to being completely dissolved, takes 0.16g graphene oxide-urethane crosslinks product to be added in cellulose casting solution, and 5d is added and urges
Agent-dibutyl tin dilaurate is allowed to sufficiently react, and is warming up to 100 DEG C of reaction 4h.The hypsokinesis of casting solution standing and defoaming will be mixed
It is poured on clean glass plate, scrapes the film for producing 50 μm of uniform thickness rapidly with scraper.Glass plate is immersed in distilled water again and is washed
Hygrometric state compound cellulose film is taken out after desolventizing, the cellulose membrane of three-phase crosslinking is obtained after natural air drying.
Embodiment 3
0.1g graphene oxide is dispersed in 100ml DMF solution by being ultrasonically treated 30min, in the guarantor of nitrogen
Under shield, the 6- methylene diisocyanate of 1.2g is added thereto uniformly mixed, and 0.05g dibutyl tin dilaurate is added
It is allowed to react 1.5h.20g [Amim] Cl and DMF (4:1) in the mixed solvent is added in the abundant dry fiber element of 1.6g, in 50 DEG C of water
It is stirred in bath to being completely dissolved, 0.25g graphene oxide-urethane crosslinks product is taken to be added in cellulose casting solution, and added
Enter 5d catalyst-dibutyl tin dilaurate sufficiently to react, is warming up to 90 DEG C of reaction 2.5h.After casting solution standing and defoaming being mixed
It is poured on clean glass plate, scrapes the film for producing 75 μm of uniform thickness rapidly with scraper.Glass plate is immersed in distilled water again
Hygrometric state compound cellulose film is taken out after eluting solvent, the cellulose membrane of three-phase crosslinking is obtained after natural air drying.
Claims (3)
1. a kind of graphene oxide-polyurethane modified cellulose three-phase cross linking membrane, composition includes cellulose, 6- methylene two
Isocyanates (HDI) and graphene oxide (GO), based on gross mass, content of cellulose is the compound cellulose diaphragm
75%~85%, 6- methylene diisocyanate content are 5%~25%, and graphene oxide content is 0.3%~5%.
2. three-phase cross linking membrane according to claim 1, which is characterized in that composite diaphragm is with a thickness of 10 μm~500 μm, hole
Rate is 30%~80%.
3. a kind of method for preparing composite membrane as defined in claim 1, which comprises the following steps:
1) graphene oxide is dispersed in n,N-Dimethylformamide (DMF) solution by 20~30min of ultrasonic treatment,
Under inert gas protection, 6- methylene diisocyanate is added thereto uniformly mixed, adds catalyst-tin dilaurate
Dibutyl tin, is warming up to 50 DEG C~100 DEG C 2~12h of reaction, and catalyst amount is 1%~5%；
2) will processing to over dry lignocellulosic material be dissolved completely in ionic liquid [Amim] Cl/DMF (4~9:1 of ratio~
6) cellulose casting solution is made in, solution temperature is 60 DEG C~100 DEG C
3) obtained graphene oxide and 6- methylene diisocyanate cross-linking products are added in cellulose casting solution sufficiently
Reaction is added catalyst-dibutyl tin dilaurate, is warming up to 85 DEG C~100 DEG C 0.5~2h of reaction, catalyst amount 1%
~5%；
4) mixing casting solution scrapes rapidly the film of uniform thickness with scraper, film is immersed distilled water after standing and defoaming
It after middle eluting solvent, is dried in room temperature to 100 DEG C, finally obtained cellulose base composite membrane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110841603A (en) * | 2019-10-29 | 2020-02-28 | 南京理工大学 | Preparation method of nano-cellulose-graphene oxide composite material |
| CN112341648A (en) * | 2020-10-28 | 2021-02-09 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170092388A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Conductive composites and compositions for producing the same, and production methods thereof |
| US20170113443A1 (en) * | 2015-10-27 | 2017-04-27 | Samsung Electronics Co., Ltd. | Conductive films and electronic devices including the same |
| CN108417765A (en) * | 2018-03-01 | 2018-08-17 | 北京林业大学 | A kind of graphene oxide modification polyurethane-cellulose lithium battery diaphragm and preparation method thereof |
-
2019
- 2019-03-11 CN CN201910181460.1A patent/CN109880056A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170092388A1 (en) * | 2015-09-24 | 2017-03-30 | Samsung Electronics Co., Ltd. | Conductive composites and compositions for producing the same, and production methods thereof |
| US20170113443A1 (en) * | 2015-10-27 | 2017-04-27 | Samsung Electronics Co., Ltd. | Conductive films and electronic devices including the same |
| CN108417765A (en) * | 2018-03-01 | 2018-08-17 | 北京林业大学 | A kind of graphene oxide modification polyurethane-cellulose lithium battery diaphragm and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110841603A (en) * | 2019-10-29 | 2020-02-28 | 南京理工大学 | Preparation method of nano-cellulose-graphene oxide composite material |
| CN112341648A (en) * | 2020-10-28 | 2021-02-09 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
| CN112341648B (en) * | 2020-10-28 | 2022-03-11 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
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