CN106519308B - A kind of preparation method of hydroxypropyl methyl cellulose cross linking membrane - Google Patents
A kind of preparation method of hydroxypropyl methyl cellulose cross linking membrane Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of hydroxypropyl methyl cellulose cross linking membrane, the corn stigma of collection is air-dried, is cut short, ground and is sieved by this method, obtain dusty raw materials, screening corn stigma is scattered in tetrabutylammonium acetate ammonium (TBAA)/acetic acid dimethylamide (DMAc) solion, while dissociateing Cellulose nanocrystal, esterification is carried out with the acetic anhydride being added dropwise to, it is nanocrystalline that cellulose acetate is made；Mixed with the DMAc lysate of hydroxypropyl methyl cellulose by above-mentioned modified cellulose is nanocrystalline, addition is without dicarboxylic anhydride, in a mold after forming, low temperature drying film forming, heating esterification and crosslinking reaction, product cleaning, it is cold it is dry after corn stigma modified cellulose blend film；The transparent film-form of the mulch as made from this method, anti-tensile with higher and draws high performance and good waterproof and oxygen barrier property.
Description
Technical field
Agricultural solid residue is utilized the present invention relates to a kind of --- corn stigma preparation has both environmentally friendly and high mechanical strong
The technology of the macromolecule transparent membrane of degree, especially a kind of nanocrystalline enhancing hydroxypropyl methyl of corn stigma cellulose acetate
The preparation method of cellulose crosslinked film belongs to natural macromolecule modification field of material technology.
Background technique
Film is begun in early stage in 19th century by development and application.The film that people used at that time is that polyolefins is thin mostly
Film, wherein high barrier polyvinyl dichloride (PVDC) film succeeded in developing the forties with DOW chemical company of the U.S. apply compared with
It is more[1], played an important role in multiple fields such as the packagings of food, medicine, chemicals, electronic device, but PVDC film is in length
Pernicious gas can be released in phase use process, it is unfavorable to human body.Hereafter, people again develop respectively polyesters, it is polyamide-based,
Polysulfones and polyethers film, wherein polyester film was carried out by Britain's ICI Company and DuPont Corporation since 1954
Industrialized production.Hereafter, two companies have developed biaxial stretch-formed mylar in succession again[2].As a whole, above-mentioned film is all
Class film is synthesized, production process and product abandonment object can all cause huge destruction to natural ecological environment, and it is thin to produce such
Raw material used in film is all oil product, is non-renewable resources.For these reasons, researchers begin look for novel
Green film material.Then, become the emphasis side of Material Field research using the research that native cellulose prepares film as raw material
One of to.
Cellulose is that nature presence is most wide, and stock number is maximum, the strongest natural polymer of renewable.If can have
Effect, the resource for fully utilizing this valuable will bring huge interests for the mankind.Contain a large amount of hydroxyls in cellulosic polymer chain
Base has formed intramolecular and the connection of intermolecular hydrogen bond, and the part of those marshallings densification forms crystal region, and arranges
Loose unordered part forms amorphous region.Exactly because the presence of crystal region is the rodlike knot that cellulose has rigidity
Structure, therefore cellulose is difficult for Conventional solvents and directly dissolves, so usual people are first translated into the form of derivative, example
Such as, carboxymethyl cellulose, hydroxymethyl, methyl cellulose, ethyl cellulose etc., are then processed and are applied, and required material is made
Material[3].Cellulose and its derivates have quite long history as film raw material, play in film producing industry very important
Effect.Especially recent years, all kinds of high-performance, functional fiber element film emerge one after another, and are in Cellulose Science research
A hot spot.The most common cellulose and its derivates film has cellulose esters film, cellulose ethers film and fiber
The esters film of plain ether[4].Hydroxypropyl methyl cellulose belongs to cellulose ethers compound, and polarity size is controllable, can be by hydroxypropyl
The molar ratio of base and methyl functional group regulates and controls.Due to non-toxic, the easy emulsification of hydroxypropyl methyl cellulose, glutinous viscosity and increase
Thick performance makes it in relatively broad applications in fields such as food processing, coating material production, mud and drug manufactures[5]。
Cellulose nanocrystal refers to cellulose crystals of one or more three-dimensional dimensions between 1 ~ 100nm[6].Nanowire
Dimension element is since its is light and there is excellent biodegradable, reproducibility and excellent mechanical performance to make reason
The filling reinforcing material and modified nano composite material thought.The method for preparing nano-cellulose has very much, for example, with sour water solution
For the chemical method of representative, Mechanical Method by way of the dissociation such as pressure, friction, heating explosion, using bacteria cellulose as representative
Bioanalysis etc..Produce Cellulose nanocrystal mechanism usually can letter and be summarized as selective removal or inhibit generate cellulose it is big
The amorphous region of strand retains or only forms the rod-like fibre cellulose crystal of nano-scale.Cellulose nanocrystal surface exists big
Activity hydroxy is measured, this hydrophilic surface layer, which results in Cellulose nanocrystal, easily to be made to form hydrogen between hydroxyl in organic solvent
It is keyed and makes that precipitating of reuniting occurs between nano-crystalline granule, and this phenomenon once occurs, it will be difficult to disperse cellulose again and receive
Meter Jing[7].Under the premise of keeping nano particle integrality, researchers are by various chemical reaction means, for example, esterification is anti-
It answers, its part or all of hydrophilic hydroxy group is modified as hydrophilic functional groups, the above-mentioned of Cellulose nanocrystal can effectively be overcome to lack
Point[8]。
Ionic liquid is primarily referred to as with low melting point (usually less than room temperature) salt.It is entirely to be deposited with ion in ionic liquid
Material composition, cation is organic constitution, and anion is inorganic constituents.Wherein, the anion pair in ionic liquid
Free hydroxyl group on cellulose macromolecule chain has very strong binding force, and during acting on cellulose, ionic liquid is advanced
Enter amorphous region to occur to be swollen and dissolve, then progresses into the crystal region of hydrogen bond network breakage, finally make ionic liquid and fibre
The hydroxy combining on plain macromolecular chain is tieed up, cellulosic molecule, which is separated from each other and is in stable state, to be present in ionic liquid, real
The dissolution of existing cellulose[9].If reaction condition is effectively controlled, for example, the usage amount of ionic liquid, reaction temperature and time etc., make
Ionic liquid acts only on cellulose amorphous region, without acting on or acting on cellulose crystallite area less, then, utilize this method
Dissociate cellulose macromolecule, prepare it is nanocrystalline very likely realize, this is also one of focus of the application.
For corn stover as one of big stalk resource in China three, yield accounts for about the 36.18% of China's stalk total output[10]。
Although the yield of corn stover is huge, its economic coefficient is low, and resource utilization rate is low, the idle waste of most corn stover or
Person's on-site incineration causes the serious wasting of resources and environmental pollution.In the laboratory research stage, raw materials used is mostly maize peel
With the corn stalks of rice, wheat, etc., and to other positions on plant, such as corn stigma is also less for Journal of Sex Research.If discarded corn stigma system
It is standby nanocrystalline at the hydrophobic fiber element that can improve film mechanical performance, the waste of waste material can be both effectively reduced,
Low-cost Cellulose nanocrystal source can be found again, improved it and utilized added value.For this purpose, the application is described in detail with corn stigma
It is raw material preparation high intensity, the environmentally friendly nanocrystalline enhancing hydroxypropyl methyl of cellulose acetate with hydroxypropyl methyl cellulose
The process flow of cellulose crosslinked film.The comprehensive utilization ratio of corn resources not only can be improved, but also attached for the height of corn stigma
It is value added that offer foundation is provided.
Bibliography
[1] Yao be loyalty .NMMO Technology for Dissolving Cellulose film the Shanghai development [D]: Donghua University, 2003.
[2] for the Qingdao research [D] of the extraction of treasure herbaceous plant cellulose, dissolution and filming performance: China Petroleum is big
It learns, 2011.
[3] Suzhou research [D] of big low-substituted hydroxypropyl cellulose preparation and its molding processibility: University Of Suzhou is opened,
2013.
[4] synthesis of Yang Yunlong cellulose esters and the Xiang Tan performance study [D]: University Of Xiangtan, 2014.
[5] P.L.Marani, G.D.Bloisi, D.F.S.Petri. Hydroxypropylmethyl
cellulose films crosslinked with citric acid for control release of nicotine
[J]. Cellulose, 2015, 22: 3907-3918.
[6] C.Liu, B.Li, H.S.Du, D.Lv, Y.D.Zhang, G.Yu, X.D.Mu, H.Peng.
Properties of nanocelllulose isolated from corncob residue using sulfuric
acid, formic acid, oxidative and mechanical methods [J]. Carbohydrate
Polymers, 151: 716-724.
[7] T.Puspasari, N.Pradeep, K.V.Peinemann. Crosslinked cellulose thin
film composite nanofiltration membranes with zero salt rejection [J]. Journal
of Membrane Science, 2015, 491: 132-137.
[8] G.Siqueira, J.Bras, A.Dufresne. Cellulosic bionanocomposites: a
review of preparation, properties and applications. Polymers, 2010, 2: 728-
765.
[9] T.Kanbayashi, H.Miyafuji. Microscopic characterization of tension
wood cell walls of Japanese beech (Faguscrenata) treated with ionic liquids
[J]. Micron, 2016, 88: 24-29.
[10] Yin Shan coral corn biomass adsorbent studies the Shanghai [D]: eastern Hua Da to the absorption of Pb in aqueous solution (II)
It learns, 2015.
Summary of the invention
Since film used at present depends on synthesis class macromolecule, environment is had both using natural polymer as matrix
The exploitation of the biomass film of friendly and good physical behavior enough basic and technology supports not yet.Therefore, this hair
Bright to provide a kind of preparation method of nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of cellulose acetate, the party utilizes jade
Rice must be initial feed with hydroxypropyl methyl cellulose, separated in solion using one kettle way and prepare corn stigma cellulose
Acetate is nanocrystalline, by hydroxypropyl methyl cellulose with it is above-mentioned it is nanocrystalline be blended, and with glutaric anhydride carry out esterification and crosslinking, preparation
Natural polymer subbase high-strength transparence film further expands the application field of cellulose and its derivates, keeps corn stigma this
Green recyclable materials obtain the utilization of high added value.
The process technology scheme for realizing that the object of the invention is taken is as follows:
(1) corn stigma separated, collect after air-dried, cut short, ground and sieved, obtain acceptable material；
(2) by stock dispersion in tetrabutylammonium acetate ammonium (TBAA)/acetic acid dimethylamide (DMAc) solion, stirring adds
Thermal release goes out Cellulose nanocrystal, and acetic anhydride is then added dropwise and carries out esterification modification, after reaction, DMAc is cleaned and is centrifuged, and is obtained
Cellulose ethanoate is nanocrystalline；
(3) hydroxypropyl methyl cellulose DMAc stirring and dissolving, lysate and the cellulose ethanoate of step (2) are received
Meter Jing is mixed in a certain ratio uniformly, and glutaric anhydride is then added, and mixed liquor is poured into mold and is shaped, low temperature drying, is formed
After solid film, heating carries out esterification and crosslinking reaction, and product film is washed repeatedly with deionized water, is freeze-dried, obtains thin
The membranaceous nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of cellulose acetate.
The present invention has both the high-intensitive and environmentally friendly nanocrystalline enhancing hydroxypropyl methyl of corn stigma cellulose acetate
The preparation method of cellulose crosslinked film, concrete operations are as follows:
(1) stock of corn stigma: corn stigma in plant after separating, collecting and air-dry processing, wherein air-drying raw material
Moisture is different according to different regions Various Seasonal air humidity and different, range of the general moisture control 8%~30%
Interior, air dry matter is cut short to 1 ~ 5cm, and is mechanically pulverized, and is sieved with 80~400 the polished standard screens, is able to powdered corn stigma
Raw material；
(2) the nanocrystalline preparation of cellulose ethanoate: a certain amount of corn stigma raw material is taken to be put into TBAA/DMAc solion
In, 10 ~ 60min is stirred under the conditions of 50 ~ 80 DEG C, is added dropwise to acetic anhydride, the reaction was continued at that same temperature 1 ~ 2.5h, wherein
Mass ratio 1:100 ~ 1:10(g/g of over dry corn stigma and TBAA/DMAc solion), tetrabutylammonium acetate ammonium/acetic acid dimethylamide
Solion is that tetrabutylammonium acetate ammonium and the acetic acid dimethylamide ratio of 1:20 ~ 1:6 in mass ratio are obtained by mixing, acetic anhydride and over dry
The mass ratio of corn stigma is 10:1 ~ 5:1(g/g), after completion of the reaction, cleaned repeatedly using DMAc, each eccentric cleaning is in revolving speed
10 ~ 30min of centrifugal action under 2000 ~ 5000rpm, until iron chloride is added in centrifuged supernatant and precipitating is not presented in heating,
It is nanocrystalline to obtain cellulose ethanoate, which is stored in DMAc from taking-up in centrifuge tube, wherein cellulose ethanoate nanometer
Brilliant and preservation acetic acid dimethylamide mass volume ratio g:mL is 1:100 ~ 1:500；
(3) preparation of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of cellulose acetate: in a certain amount of DMAc
Middle addition hydroxypropyl methyl cellulose is stirred to dissolution, hydroxypropyl methyl cellulose be dissolved in the concentration in acetic acid dimethylamide be 5 ~
15g/L；Meanwhile the nanocrystalline dimethylamino acetyl amine aqueous solution of the cellulose ethanoate of step (2) being surpassed under the power of 500 ~ 1000w
1.5 ~ 2.5h of sound wave effect, and be added in hydroxypropyl methyl cellulose lysate, wherein hydroxypropyl methyl cellulose and cellulose
The mass volume ratio of the nanocrystalline dimethylamino acetyl amine aqueous solution of acetic acid esters is 1:10 ~ 1:20(g/mL), the system being uniformly mixed herein
In continuously add crosslinking agent --- glutaric anhydride, dosage and hydroxypropyl methyl cellulose mass ratio are 0.01:1 ~ 0.1:1(g/
G), after mixing evenly, pour into the mold that diameter is 5~100cm, the oven drying 12 ~ form solid film for 24 hours at 50 ~ 70 DEG C,
Then 5 ~ 15min of esterification and crosslinking at 150 ~ 180 DEG C, cross linking membrane are washed repeatedly with deionized water, and freeze-drying obtains thin
The membranaceous nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate.
The beneficial effects of the present invention are: to rarely have the agricultural wastes corn stigma of higher value application as Cellulose nanocrystal
Source, it is nanocrystalline that cellulose acetate is converted for corn stigma in solion by one kettle way, gained is nanocrystalline and hydroxyl
Propyl methocel is blended, and is reacted by the esterification and crosslinking of glutaric anhydride, is made high-intensitive, environmental friendly corn must fiber
Plain acetate is nanocrystalline/hydroxypropyl methyl cellulose blend film.With the development of membrane science, the new material of various function admirables is not
It is disconnected to occur, every field has been had been widely used with the functional membrane of cellulose matrix.According to the progress of science and technology and society's hair
Open up the requirements at the higher level to membrane material characteristic, such as environmentally degradable, low energy consumption, diversification etc., native cellulose based composites
Very big vitality is embodied.Modified cellulose blend film has the general character of synthetic polymeric kind film, has high tenacity, tension
Power, heat preservation, it is fresh-keeping, light transmission power is strong, purposes is wide the advantages that, can be played in multiple fields such as agricultural, industry, food, medicine good
Effect.Meanwhile the modified cellulose blend membraness are also equipped with excellent hypotoxicity, environmental degradability and cheap price etc.
Advantage is novel, the green functional material of one kind of mainstream development now, the effective use for being embodied as corn stigma of such mulch
A feasible scheme is provided, the functionalization exploitation for also abandoning stalk for other agricultures provides certain basis early period.
Specific embodiment
Below with reference to embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
Embodiment 1: the preparation side of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of this corn stigma cellulose acetate
Method, concrete operations are as follows:
(1) melting process of corn stigma
Corn stigma is separated and is collected from plant, and by air-drying processing, wherein the water content for air-drying raw material is 8%,
Then air dry matter is cut short to 5cm, and is mechanically pulverized, and is sieved with standard screen, and 80 mesh screens were taken, but only 150 mesh screen
Part be acceptable material；
(2) the nanocrystalline preparation process of cellulose ethanoate
Over dry corn stigma raw material (because air-drying raw aqueous 8%, claiming 0.1/(100-8) %=0.11g of 0.1g is taken to air-dry material) it puts
Enter in the TBAA/DMAc mixed solution (0.14gTBAA and 0.86gDAMc) of 1.0g, stir 60min under the conditions of 50 DEG C, is added dropwise
Enter 0.5g acetic anhydride, the reaction was continued at that same temperature, and 1h is carried out repeatedly using DMAc under the action of the centrifugal after completion of the reaction
Cleaning, wherein centrifugal rotational speed 2000rpm acts on 10min every time, until iron chloride is added for centrifuged supernatant and heating is not in
Until now precipitating, obtain that cellulose ethanoate is nanocrystalline, which is transferred in beaker with the DMAc of 10mL and is saved；
(3) preparation process of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate
0.5g hydroxypropyl methyl cellulose is added in the DMAc of 100mL to stir to dissolution, is allowed to concentration and controls in 5g/L,
Meanwhile ultrasonic wave acts under the power of 500w by the nanocrystalline dimethylamino acetyl amine aqueous solution of the cellulose ethanoate of step (2)
1.5h, and be all added in hydroxypropyl methyl cellulose lysate, 0.005g is continuously added in uniformly mixed system herein
Glutaric anhydride pours into the mold that diameter is 5cm, oven drying 12h forms solid film at 50 DEG C, then after mixing evenly
The esterification and crosslinking 5min at 150 DEG C, cross linking membrane are washed repeatedly with deionized water, and freeze-drying obtains film-form corn stigma
The nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of cellulose acetate；
(4) character of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate
The measurement of thin film physics intensity: being anti-tensile using universal testing machine measurement result according to ASTM D638 test method
Intensity and to draw high coefficient be respectively 121MPa and 582%.
The measurement of film clarity: under the conditions of 600nm, the transparency of film is measured using ultraviolet-visible absorption spectroscopy,
It as a result is 89.7%.
The measurement of film hydrophobicity performance: using HARKE-SPCA contact angle instrument detection deionization droplet on film
Contact angle, the hydrophobic effect of film is measured by the index, and result is 56.8 °.
The measurement of film oxygen transmission rate: according to ASTM D-3985 standard, under 0% damp condition, MOCON Oxtran is utilized
2/21 oxygen permeameter measures the oxygen transmission rate of film, as a result are as follows: 0.0812cm3 μm m-2 day-1 kPa-1。
Embodiment 2: the preparation side of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of this corn stigma cellulose acetate
Method, concrete operations are as follows:
(1) melting process of corn stigma
Corn stigma is separated and is collected from plant, and by air-drying processing, wherein the water content for air-drying raw material is
20%, then air dry matter is cut short to 3cm, and is mechanically pulverized, and is sieved with standard screen, and 180 mesh screens were taken, but only 300 mesh
The part of sieve is acceptable material；
(2) the nanocrystalline preparation process of cellulose ethanoate
Over dry corn stigma raw material (because air-drying raw aqueous 20%, claiming 0.5/(100-20) %=0.63g of 0.5g is taken to air-dry material)
It is put into the TBAA/DMAc mixed solution (1.8gTBAA and 28.2gDAMc) of 30g, stirs 30min under the conditions of 65 DEG C, be added dropwise
Enter 4.0g acetic anhydride, the reaction was continued at that same temperature, and 2h is carried out repeatedly using DMAc under the action of the centrifugal after completion of the reaction
Cleaning, wherein centrifugal rotational speed 4000rpm acts on 20min every time, until iron chloride is added for centrifuged supernatant and heating is not in
Until now precipitating, obtain that cellulose ethanoate is nanocrystalline, which is transferred in beaker with the DMAc of 150mL and is saved；
(3) preparation process of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate
10g hydroxypropyl methyl cellulose is added in the DMAc of 1000mL to stir to dissolution, is allowed to concentration control in 10g/
L, meanwhile, by the nanocrystalline DMAc solution of the cellulose acetate of step (2), ultrasonic wave acts on 2.0h under the power of 800w, and complete
Portion is added in hydroxypropyl methyl cellulose lysate, is continuously added 0.08g glutaric anhydride in uniformly mixed system herein, is stirred
After mixing uniformly, pour into the mold that diameter is 50cm, oven drying 20h forms solid film at 60 DEG C, then the ester at 165 DEG C
Change crosslinking 10min, cross linking membrane is washed repeatedly with deionized water, is freeze-dried, is obtained film-form corn stigma cellulose acetate
The nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of ester；
(4) character of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate
The measurement of thin film physics intensity: being anti-tensile using universal testing machine measurement result according to ASTM D638 test method
Intensity and to draw high coefficient be respectively 165MPa and 801%.
The measurement of film clarity: under the conditions of 600nm, the transparency of film is measured using ultraviolet-visible absorption spectroscopy,
It as a result is 92.0%.
The measurement of film hydrophobicity performance: using HARKE-SPCA contact angle instrument detection deionization droplet on film
Contact angle, the hydrophobic effect of film is measured by the index, and result is 70.2 °.
The measurement of film oxygen transmission rate: according to ASTM D-3985 standard, under 0% damp condition, MOCON Oxtran is utilized
2/21 oxygen permeameter measures the oxygen transmission rate of film, as a result are as follows: 0.0255cm3 μm m-2 day-1 kPa-1。
Embodiment 3: the preparation side of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of this corn stigma cellulose acetate
Method, concrete operations are as follows:
(1) melting process of corn stigma
Corn stigma is separated and is collected from plant, and by air-drying processing, wherein the water content for air-drying raw material is
30%, then air dry matter is cut short to 1cm, and is mechanically pulverized, and is sieved with standard screen, and 220 mesh screens were taken, but only 400 mesh
The part of sieve is acceptable material；
(2) the nanocrystalline preparation process of cellulose ethanoate
Over dry corn stigma raw material (because air-drying raw aqueous 30%, claiming 1/(100-30) %=1.43g of 1g is taken to air-dry material) it is put into
In the TBAA/DMAc mixed solution (4.8gTBAA and 96.0gDAMc) of 100g, 10min is stirred under the conditions of 80 DEG C, is added dropwise to
10g acetic anhydride, the reaction was continued at that same temperature, and 2.5h is carried out repeatedly using DMAc under the action of the centrifugal after completion of the reaction
Cleaning, wherein centrifugal rotational speed 5000rpm acts on 30min every time, until iron chloride is added for centrifuged supernatant and heating is not in
Until now precipitating, obtain that cellulose ethanoate is nanocrystalline, which is transferred in beaker with the DMAc of 500mL and is saved；
(3) preparation process of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate
25g hydroxypropyl methyl cellulose is added in the DMAc of 1666mL to stir to dissolution, is allowed to concentration control in 15g/
L, meanwhile, by the nanocrystalline DMAc solution of the cellulose acetate of step (2), ultrasonic wave acts on 2.5h under the power of 1000w, and
It is all added in hydroxypropyl methyl cellulose lysate, continuously adds 2.5g glutaric anhydride in uniformly mixed system herein,
After mixing evenly, it pours into the mold that diameter is 100cm, oven drying forms solid film for 24 hours at 70 DEG C, then at 180 DEG C
Lower esterification and crosslinking 15min, cross linking membrane are washed repeatedly with deionized water, and freeze-drying obtains film-form corn stigma cellulose
The nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of acetate；
(4) character of the nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate
The measurement of thin film physics intensity: being anti-tensile using universal testing machine measurement result according to ASTM D638 test method
Intensity and to draw high coefficient be respectively 177MPa and 692%.
The measurement of film clarity: under the conditions of 600nm, the transparency of film is measured using ultraviolet-visible absorption spectroscopy,
It as a result is 85.8%.
The measurement of film hydrophobicity performance: using HARKE-SPCA contact angle instrument detection deionization droplet on film
Contact angle, the hydrophobic effect of film is measured by the index, and result is 61.7 °.
The measurement of film oxygen transmission rate: according to ASTM D-3985 standard, under 0% damp condition, MOCON Oxtran is utilized
2/21 oxygen permeameter measures the oxygen transmission rate of film, as a result are as follows: 0.0995cm3 μm m-2 day-1 kPa-1。
Claims (2)
1. a kind of preparation method of hydroxypropyl methyl cellulose cross linking membrane, which is characterized in that carry out as follows:
(1) corn stigma separated, collect after air-dried, cut short, ground and sieved stock, powdered corn stigma is scattered in four fourths
In base ammonium acetate/acetic acid dimethylamide solion, by stirring and Cellulose nanocrystal is isolated in heating, acetic anhydride is then added dropwise
It carries out esterification modification to be cleaned and be centrifugated with acetic acid dimethylamide after reaction, it is nanocrystalline to obtain cellulose ethanoate；
(2) first by hydroxypropyl methyl cellulose acetic acid dimethylamide stirring and dissolving, the cellulose acetate of lysate and step (1)
Ester is nanocrystalline to be mixed in proportion, and glutaric anhydride is then added, mixed liquor is poured into mold and is shaped, low temperature drying, is formed
After solid film, heating carries out esterification and crosslinking reaction, and product film is washed repeatedly with deionized water, is freeze-dried, obtains thin
The membranaceous nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane of corn stigma cellulose acetate；
The low temperature drying is dry at 50 ~ 70 DEG C.
2. the preparation method of hydroxypropyl methyl cellulose cross linking membrane according to claim 1, it is characterised in that concrete operations
It is as follows:
(1) corn stigma of collection is carried out air-drying processing, is smashed and ground after cutting short, sieved, be able to 80~400 the polished standard screens
Powdered corn stigma raw material；
(2) the corn stigma raw material after screening is uniformly mixed with tetrabutylammonium acetate ammonium/acetic acid dimethylamide solion, 50 ~ 80
10 ~ 60min is stirred under the conditions of DEG C, is added dropwise to acetic anhydride, the reaction was continued at that same temperature 1 ~ 2.5h, after completion of the reaction repeatedly
With acetic acid dimethylamide eccentric cleaning, 2000 ~ 5000rpm is centrifuged 10 ~ 30min every time, until iron chloride is added simultaneously in centrifuged supernatant
Until precipitating is not presented in heating, obtain that cellulose ethanoate is nanocrystalline, and product is stored in acetic acid dimethylamide, wherein over dry corn
It must be 1:100 ~ 1:10, tetrabutylammonium acetate ammonium/dimethylamino acetyl with tetrabutylammonium acetate ammonium/acetic acid dimethylamide solion mass ratio
Amine solion is that tetrabutylammonium acetate ammonium and the acetic acid dimethylamide ratio of 1:20 ~ 1:6 in mass ratio are obtained by mixing, acetic anhydride with it is exhausted
The mass ratio of dry corn stigma is 10:1 ~ 5:1, the nanocrystalline mass volume ratio g that acetic acid dimethylamide is used with preservation of cellulose ethanoate:
ML is 1:100 ~ 1:500；
(3) first by hydroxypropyl methyl cellulose in acetic acid dimethylamide stirring and dissolving, meanwhile, by the cellulose acetate of step (2)
The nanocrystalline dimethylamino acetyl amine aqueous solution of ester is added to hydroxypropyl after ultrasonic wave under the power of 500 ~ 1000w acts on 1.5 ~ 2.5h
In methylcellulose lysate, it is stirring evenly and then adding into crosslinking agent glutaric anhydride, wherein hydroxypropyl methyl cellulose is dissolved in two
Concentration in first and second amides is 5 ~ 15g/L, and the hydroxypropyl methyl cellulose acetic acid dimethylamide nanocrystalline with cellulose ethanoate is molten
The mass volume ratio g:mL of liquid is 1:10 ~ 1:20, and glutaric anhydride and hydroxypropyl methyl cellulose mass ratio are 0.01:1 ~ 0.1:1；
After mixing evenly, it pours into mold, dry 12 at 50 ~ 70 DEG C ~ solid film is formed for 24 hours, it is then esterified and hands at 150 ~ 180 DEG C
Join 5 ~ 15min, cross linking membrane is washed repeatedly with deionized water, is freeze-dried, is obtained film-form corn stigma cellulose acetate
Nanocrystalline enhancing hydroxypropyl methyl cellulose cross linking membrane.
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