CN104512072A - A separating composite film and a preparing method thereof - Google Patents
A separating composite film and a preparing method thereof Download PDFInfo
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- CN104512072A CN104512072A CN201310449498.5A CN201310449498A CN104512072A CN 104512072 A CN104512072 A CN 104512072A CN 201310449498 A CN201310449498 A CN 201310449498A CN 104512072 A CN104512072 A CN 104512072A
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- counterdie
- polysulfones
- laminated film
- cellulose
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- 238000000034 method Methods 0.000 title abstract description 17
- 239000002131 composite material Substances 0.000 title abstract description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 99
- 229920002678 cellulose Polymers 0.000 claims abstract description 62
- 239000001913 cellulose Substances 0.000 claims abstract description 62
- 238000002360 preparation method Methods 0.000 claims description 34
- 239000006185 dispersion Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 23
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- AKKLAJYCGVIWBS-UHFFFAOYSA-N O=[N].CC1(C)CCCC(C)(C)N1 Chemical group O=[N].CC1(C)CCCC(C)(C)N1 AKKLAJYCGVIWBS-UHFFFAOYSA-N 0.000 claims description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002419 bulk glass Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/10—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A separating composite film and a preparing method thereof are provided. The separating composite film comprises a polysulfone base film and a cellulose layer on a surface of the polysulfone base film. The surface where the cellulose layer and the polysulfone base film are in contact is carboxylated cellulose. The composite film has good separation performance for gases and vapor. In addition, the composite film is transparent, and can be bended freely, thus largely broadening the application scope of the composite film. The preparing method of the composite film is simplified in process, convenient in operation, easily available in raw materials, low in production cost, and high in product yield.
Description
Technical field
The invention belongs to macromolecule membrane technical field, be specifically related to a kind of obstruct laminated film and preparation method thereof.
Background technology
Have the features such as excellent mechanical strength, the close property of resistance to compression, chemical stability, heat resistance due to polysulfones material, it has certain hydrophobicity, at present general chemical modification is carried out to its surface after, be used as super hydrophilic film, be used widely in hyperfiltration technique.But in fact, the hydrophobicity of polysulfones material is good not enough, and it is bad to the barrier property of gas and water, can not be applied in packaging obstruct field as plastic barrier film.
At present, in prior art, polysulfones plastic sheeting is when being used as gas barrier film, generally can plate one deck aluminium or other inorganic oxide such as metal or aluminium oxide again in Plastic film surface, forms laminated film.But this laminated film, easily produce pin hole or crackle in molding procedure, it is still poor to the barrier of gas and water.
Summary of the invention
The invention solves the technical problem that the polysulfones plastic sheeting that exists in prior art or the laminated film barrier to gas and water is poor.
The invention provides a kind of obstruct laminated film, described obstruct laminated film comprises polysulfones counterdie and is positioned at the cellulose layer on polysulfones counterdie surface, and the one side that described cellulose layer contacts with polysulfones counterdie is carboxylated cellulose element.
Present invention also offers the preparation method of described obstruct laminated film, comprise the following steps:
S10, polysulfones, organic solvent to be mixed in a heated condition with curing agent, obtain homodisperse counterdie solution; Then the striking on glass of counterdie solution is formed primary membrane, after solidifying, obtain polysulfones counterdie;
S20, cellulose is scattered in water, then adds oxidant, be stirred to and obtain transparent dispersion system; Described oxidant is 2,2,6,6-tetramethyl piperidine-nitrogen-oxide;
S30, the polysulfones counterdie of step S10 to be contacted with the transparent dispersion system of step S20, after drying, obtain described obstruct laminated film.
Obstruct laminated film provided by the invention, by covering one deck cellulose again on hydrophobicity imperfect polysulfones counterdie surface, and by carrying out surface modification to cellulose, ensure that surface fibre element has good adhesion with bottom polysulfones on the one hand, fine and close cover layer is formed on polysulfones surface, on the other hand modification is carried out to cellulose self structure and improve its barrier property further, thus effectively can ensure the good barrier of described obstruct laminated film to gas and water.Meanwhile, obstruct laminated film provided by the invention is transparent material, and can arbitrarily bend, and considerably increases its application.The preparation method of obstruct laminated film provided by the invention, technique simplifies, and easy to operate, raw material is easy to get, and production cost is low, and product yield is high.
Detailed description of the invention
In currently available technology, polysulfone material is generally be used as super hydrophilic film, mainly passes through its modifying surface, such as, at its surface grafting hydrophilic active group, thus improves its transmitance to water.Such as, have by first preparing methylolation polysulfones to polysulfone material modification in prior art, improve its reactivity, and then in acid condition, mix with polysulfones with hydroxyethylcellulose, the laminated film surface obtained, owing to introducing great amount of hydroxy group active group, therefore has good hydrophily, makes it can be widely used in hydrophilic ultra-filtration and separation.
And in the present invention, then just in time contrary with research of the prior art, namely the permeability of polysulfone material to water is not only increased, reduce its transmitance to water on the contrary further, thus preparation has the film of good barrier to steam and gas, make this film can the various packaging field of extensive use, hinder air and moisture to enter into package interior, anti-oxidation or humidity cause product deterioration.Particularly, the present inventor finds, common wood pulp and the cellulose contained by paper pulp, it has the characteristic not easily through oxygen and moisture.But cellulose and polysulfone material are generally difficult to combine, adopt general associated methods of the prior art, more hydrophilic radicals can be introduced on the contrary, cause the water vapor rejection performance of the composite finally obtained poorer.Therefore, the present inventor passes through creative work, find to adopt method provided by the invention to carry out modifiedly being combined with polysulfone material again to cellulose, not only can improve the adhesion both it, while can also ensure the excellent barrier properties of final composite to steam and gas.Particularly, the invention provides a kind of obstruct laminated film, described obstruct laminated film comprises polysulfones counterdie and is positioned at the cellulose layer on polysulfones counterdie surface, and the one side that described cellulose layer contacts with polysulfones counterdie is carboxylated cellulose element.
Obstruct laminated film provided by the invention, by covering one deck cellulose again on hydrophobicity imperfect polysulfones counterdie surface, and by carrying out surface modification to cellulose, ensure that surface fibre element has good adhesion with bottom polysulfones on the one hand, fine and close cover layer is formed on polysulfones surface, on the other hand modification is carried out to cellulose self structure and improve its barrier property further, thus effectively can ensure the good barrier of described obstruct laminated film to gas and water.Meanwhile, obstruct laminated film provided by the invention is transparent material, and can arbitrarily bend, and considerably increases its application.
Under preferable case, in the present invention, the thickness of described polysulfones counterdie is 20 ~ 60 microns.
In the present invention, described cellulose layer can be positioned at a surface (namely one side covers cellulose) of polysulfones counterdie, also can be positioned at two surfaces (namely two-sided cover cellulose) of polysulfones counterdie.Under preferable case, two surfaces up and down of described polysulfones counterdie all have cellulose layer, now, intercept steam completely, gas contacts with the polysulfones counterdie of internal layer by bilevel cellulose layer, thus increase the barrier property of laminated film further.
In the present invention, the thickness of the cellulose layer on polysulfones counterdie surface is too little, then can not play the effect intercepting steam, gas and contact with polysulfones counterdie, and too conference increases film thickness, increase material cost and limit its use field, therefore, as a kind of preferred embodiment of the present invention, the thickness of the cellulose layer of the one side of described polysulfones counterdie is 5 ~ 10 microns.Namely described obstruct laminated film is one side when covering cellulosic structure, and the thickness of its surface fiber element layer is 5 ~ 10 microns; And when described obstruct laminated film be two-sided cover cellulosic structure time, the thickness of its upper and lower two surperficial cellulose layers is 5 ~ 10 microns independently of one another.
Present invention also offers the preparation method of described obstruct laminated film, comprise the following steps:
S10, polysulfones, organic solvent to be mixed in a heated condition with curing agent, obtain homodisperse counterdie solution; Then the striking on glass of counterdie solution is formed primary membrane, after solidifying, obtain polysulfones counterdie;
S20, cellulose is scattered in water, then adds oxidant, be stirred to and obtain transparent dispersion system; Described oxidant is 2,2,6,6-tetramethyl piperidine-nitrogen-oxide;
S30, the polysulfones counterdie of step S10 to be contacted with the transparent dispersion system of step S20, after drying, obtain described obstruct laminated film.
The preparation method of obstruct laminated film provided by the invention, technique simplifies, and easy to operate, raw material is easy to get, and production cost is low, and product yield is high.
Particularly, first according to method of the present invention, preparation counterdie solution, then scrapes and makes primary membrane, can obtain polysulfones counterdie after solidifying.Wherein, the organic solvent adopted during preparation counterdie solution is the good solvent of polysulfones in prior art, such as, can be selected from least one in N-methyl-pyrrolidon, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), but be not limited to this.Described curing agent is selected from least one in polyethylene glycol, polyvinylpyrrolidone, propane diols, for promoting that the polysulfones in solution forms rete.
The consumption of organic solvent, without the need to excessive, only needs polysulfones fully to be dissolved.Under preferable case, with the polysulfones of 10 weight portions for benchmark, the consumption of organic solvent is 30 ~ 90 weight portions, and the consumption of curing agent is 1 ~ 5 part of weight portion.
Because the chemical stability of polysulfones is better, therefore for shortening the process time, promoting the dissolving of polysulfones, as a kind of preferred embodiment of the present invention, the step mixed under described heating condition comprises: polysulfones, organic solvent are first mixed at 70 ~ 80 DEG C with curing agent, be then stirred to the rotating speed of 100 ~ 300r/min and obtain homodisperse solution.
For preventing there is bubble in the primary membrane of formation, reducing the barrier property of laminated film, in the present invention, before being also included in striking film forming, counterdie solution being carried out to the step of deaeration.Particularly, the step of described deaeration comprises: counterdie solution is left standstill 8 ~ 24h, to slough the bubble in counterdie solution at 50 ~ 60 DEG C.
Wherein, the step that the striking on glass of counterdie solution forms primary membrane be well known to those skilled in the art, the present invention is not particularly limited, specifically comprise: counterdie solution is fallen on glass, scrape with scraper and make film, and leave standstill 1 ~ 6min at room temperature, obtain described primary membrane.Wherein, the glass adopted is the various glass plates that in prior art, masking is conventional, and the present invention does not have particular/special requirement.After obtaining primary membrane, then entirety is solidified, and can obtain polysulfones counterdie.Particularly, the step of solidifying comprises: primary membrane is put into frozen water together with bulk glass and soaks 6 ~ 10min, then soak through room temperature washing, finally dry 2 ~ 4h at 50 ~ 70 DEG C.
According to method of the present invention, then prepare cellulosic dispersion, specifically comprise: cellulose is scattered in water, then adds oxidant, be stirred to and obtain transparent dispersion system.Due to the organic solvent that cellulose is water insoluble and general, after therefore being mixed with water by cellulose in the present invention, agitator need be adopted to stir, make formation cellulose-water slurry.Under preferable case, speed of agitator is now 50 ~ 100r/min, and mixing time is 5 ~ 10min.
Then in cellulose-water slurry, add oxidant, now suspension can be gel state, now needs to adopt agitator to continue to stir.In whipping process, the part of hydroxyl contained by cellulose can be converted into carboxyl by oxidant.Along with the increase of carboxyl-content, introduce highdensity anionic property carboxyl on cellulose, because electric charge repels each other, gel state system originally can be made to be converted into and be uniformly dispersed and stable transparent dispersion system, be the cellulose system containing partial chemical modification.Meanwhile, after cellulose surface carboxylated, also help and to be follow-uply combined with polysulfones counterdie.But the consumption of oxidant is too much unsuitable, otherwise cellulose can be caused to degrade in a large number, and reduces the mechanical strength of cellulose layer.Therefore, in the present invention, with the cellulose of 10 weight portions for benchmark, the consumption of water is 10 ~ 40 weight portions, and the consumption of oxidant is 1 ~ 3 weight portion.
In the present invention, the oxidant adopted is 2,2,6,6-tetramethyl piperidine-nitrogen-oxide (being called for short TEMPO), and it is a kind of cyclic compound with stable nitrogen-oxygen free radical structure.In the present invention, described oxidant TEMPO directly can adopt commercial products, and the present invention is not particularly limited.
According to preparation method provided by the invention, then polysulfones counterdie is contacted with the aforementioned transparent dispersion system obtained, obstruct laminated film provided by the invention after drying, can be obtained.Dry condition comprises: temperature is 60 ~ 90 DEG C, and the time is 20 ~ 40min.
In the present invention, the different ways of contact, can obtain the obstruct laminated film of different structure.Such as, when preparing one side and covering the obstruct laminated film of cellulose layer, only the one side of polysulfones counterdie need be contacted with transparent dispersion system, such as this transparent dispersion system can be toppled in right amount a part in the upper surface of the polysulfones counterdie of horizontal positioned, one side can be obtained after drying and cover cellulosic polysulfones counterdie composite construction.Or the polysulfones counterdie after solidifying is not departed from from glass, and impregnated in transparent dispersion system together with bulk glass, now due to the existence of glass, polysulfones counterdie is only contacted with transparent dispersion system on a surface, also can form one side and cover fibrolaminar obstruct laminated film, finally depart from glass plate again.
As previously mentioned, in the present invention, described obstruct laminated film is preferably two-sided covers cellulosic polysulfones counterdie composite construction, now, the step that polysulfones counterdie contacts with transparent dispersion system is: by polysulfones counterdie mass-impregnation in transparent dispersion system, after drying, obtains the polysulfones counterdie that upper and lower two surfaces all have cellulose layer.Under preferable case, dip time is 6 ~ 15min.
In polysulfones counterdie and transparent dispersion system contact process, the cellulose of the part carboxylated in transparent dispersion system is by the hydroxyl condensation in carboxyl and polysulfones structure, thus ensure, between surface fibre element layer and internal layer polysulfones counterdie, there is good adhesion, make to combine densification between two-layer interface; The one side do not contacted with polysulfones counterdie of surface fibre element layer is still fibrillation element structure simultaneously, and it can form fine and close cover layer, prevents steam, gas permeation cellulose layer from contacting with polysulfones counterdie, thus greatly strengthens the barrier property intercepting laminated film.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
(1) polysulfones counterdie preparation:
Polysulfones 20g, dimethylacetylamide 170g, polyethylene glycol 10g are put into beaker, adopt water-bath 70 DEG C of heated at constant temperature, stir with the rotating speed of 100r/min, until solution homogeneous clear can stop, obtain counterdie solution, and be placed in 50 DEG C, baking oven heating standing and defoaming 8h.By the counterdie solution after this deaeration, adopt scraper striking film forming on a glass, and place 6min in atmosphere, obtain primary membrane, then primary membrane is put into frozen water together with glass plate entirety and soak 6min, soak through room temperature washing after taking-up, then vacuum drying oven is proceeded to, 50 DEG C of dry 2h, slough glass plate, obtain the polysulfones counterdie that thickness is 30 microns.
(2) transparent dispersion system preparation:
30g cellulose is put into beaker, then adds 65g deionized water, stir after 5min with the rotating speed of 50r/min and obtain suspension, in suspension, add 5g oxidant TEMPO, continue to be stirred to the rotating speed of 100r/min and obtain transparent dispersion system.
(3) preparation of laminated film S1 is intercepted:
The polysulfones counterdie that step (1) obtains is soaked in the transparent dispersion system of step (2), soak time is 8min, dry 20min at 60 DEG C, baking oven is proceeded to after taking-up, obtain the two-sided obstruct laminated film S1 covering cellulose layer of the present embodiment, in this obstruct laminated film S1, the thickness of upper and lower two surperficial cellulose layers is 6 microns.
Embodiment 2
(1) polysulfones counterdie preparation:
Polysulfones 25g, N-methyl-pyrrolidon 70g, propane diols 5g are put into beaker, adopt water-bath 80 DEG C of heated at constant temperature, stir with the rotating speed of 200r/min, until solution homogeneous clear can stop obtaining counterdie solution, and be placed in 60 DEG C, baking oven heating standing and defoaming 10h.By the counterdie solution after this deaeration, adopt scraper striking film forming on a glass, and place 4min in atmosphere, obtain primary membrane, then primary membrane is put into frozen water 8min together with glass plate entirety, soak through room temperature washing after taking-up, then vacuum drying oven is proceeded to, 60 DEG C of dry 3h, slough glass plate, obtain the polysulfones counterdie that thickness is 34 microns.
(2) preparation of dispersion soln:
20g cellulose is put into beaker, then adds 77g deionized water, stir 6min with the rotating speed of 100r/min and obtain suspension, in suspension, add 3g oxidant TEMPO, continue to be stirred to the rotating speed of 80r/min and obtain transparent dispersion system.
(3) preparation of laminated film S2 is intercepted:
The polysulfones counterdie that step (1) obtains is soaked in the transparent dispersion system of step (2), soak time is 10min, baking oven 80 DEG C of dry 30min are proceeded to after taking-up, obtain the two-sided obstruct laminated film S2 covering cellulose layer of the present embodiment,, in this obstruct laminated film S2, the thickness of upper and lower two surperficial cellulose layers is 7.5 microns.
Embodiment 3
(1) polysulfones counterdie preparation:
Polysulfones 15g, dimethyl sulfoxide (DMSO) 82g, propane diols 3g are put into beaker, adopt water-bath 80 DEG C of heated at constant temperature, stir with the rotating speed of 150r/min, until solution homogeneous clear can stop, obtain counterdie solution, and be placed in 80 DEG C, baking oven heating standing and defoaming 24h.By the counterdie solution after this deaeration, adopt scraper striking film forming on a glass, and place 6min in atmosphere, obtain primary membrane, then primary membrane is put into frozen water together with glass plate entirety and soak 10min, soak through room temperature washing after taking-up, then vacuum drying oven is proceeded to, 60 DEG C of dry 3h, slough glass plate, obtain the polysulfones counterdie that thickness is 35 microns.
(2) transparent dispersion system preparation:
40g cellulose is put into beaker, then adds 55g deionized water, stir after 6min with the rotating speed of 100r/min and obtain suspension, in suspension, add 5g oxidant TEMPO, continue to be stirred to the rotating speed of 80r/min and obtain transparent dispersion system.
(3) preparation of laminated film S3 is intercepted:
The polysulfones counterdie that step (1) obtains is soaked in the transparent dispersion system of step (2), soak time is 15min, baking oven 80 DEG C of dry 30min are proceeded to after taking-up, obtain the two-sided obstruct laminated film S3 covering cellulose layer of the present embodiment, in this obstruct laminated film S3, the thickness of upper and lower two surperficial cellulose layers is 10 microns.
Embodiment 4
(1) polysulfones counterdie preparation:
Polysulfones 20g, dimethylacetylamide 170g, polyethylene glycol 10g are put into beaker, adopt water-bath 70 DEG C of heated at constant temperature, stir with the rotating speed of 100r/min, until solution homogeneous clear can stop, obtain counterdie solution, and be placed in 50 DEG C, baking oven heating standing and defoaming 8h.By the counterdie solution after this deaeration, adopt scraper striking film forming on a glass, and place 6min in atmosphere, obtain primary membrane, then primary membrane is put into frozen water together with glass plate entirety and soak 6min, soak through room temperature washing after taking-up, then proceed to vacuum drying oven, 50 DEG C of dry 2h, obtain the polysulfones counterdie that thickness is 30 microns.
(2) transparent dispersion system preparation:
30g cellulose is put into beaker, then adds 65g deionized water, stir after 5min with the rotating speed of 50r/min and obtain suspension, in suspension, add 5g oxidant TEMPO, continue to be stirred to the rotating speed of 100r/min and obtain transparent dispersion system.
(3) preparation of laminated film S1 is intercepted:
Polysulfones counterdie step (1) obtained is soaked in together with glass plate entirety in the transparent dispersion system of step (2), soak time is 8min, dry 20min at 60 DEG C, baking oven is proceeded to after taking-up, then glass plate is sloughed, the one side obtaining the present embodiment covers the obstruct laminated film S4 of cellulose layer, and the cellulose layer thickness of this obstruct laminated film S4 mesexine is 6 microns.
Comparative example 1
Polysulfones 20g, dimethylacetylamide 170g, polyethylene glycol 10g are put into beaker, adopt water-bath 70 DEG C of heated at constant temperature, stir with the rotating speed of 100r/min, until solution homogeneous clear can stop, obtain counterdie solution, and be placed in 50 DEG C, baking oven heating standing and defoaming 8h.By the counterdie solution after this deaeration, adopt scraper striking film forming on a glass, and place 6min in atmosphere, obtain primary membrane, then primary membrane is put into frozen water together with glass plate entirety and soak 6min, soak through room temperature washing after taking-up, then proceed to vacuum drying oven, 50 DEG C of dry 2h, obtain the polysulfones counterdie that thickness is 30 microns.Then using overall as base material for this attachment polysulfones counterdie on a glass, continue plating layer of metal aluminium on its polysulfones counterdie surface, thickness of coating 15 microns, obtains the obstruct laminated film DS1 of this comparative example after sloughing glass plate.
Performance test
1, OTR oxygen transmission rate test
The equal-pressure method in ASTM D3985-1995 is adopted to test each obstruct laminated film S1-S4 and DS1 to the transmitance of oxygen.
2, testing vapor transmission
The cup type method in GB/T1037-1988 is adopted to test each obstruct laminated film S1-S4 and DS1 to the transmitance of oxygen.
Test result is as shown in table 1.
Table 1
。
As can be seen from the test result of upper table 1, adopting the obstruct laminated film that preparation method provided by the invention prepares, is 0.9 ~ 2.3% to the transmitance of oxygen, is 3 ~ 5%, is obviously better than the sample of comparative example to the transmitance of steam.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. intercept a laminated film, it is characterized in that, described obstruct laminated film comprises polysulfones counterdie and is positioned at the cellulose layer on polysulfones counterdie surface, and the one side that described cellulose layer contacts with polysulfones counterdie is carboxylated cellulose element.
2. obstruct laminated film according to claim 1, is characterized in that, the thickness of described polysulfones counterdie is 20 ~ 60 microns.
3. obstruct laminated film according to claim 1, is characterized in that, two surfaces up and down of described polysulfones counterdie all have cellulose layer.
4. obstruct laminated film according to claim 3, is characterized in that, the thickness of the cellulose layer of the one side of described polysulfones counterdie is 5 ~ 10 microns.
5. the preparation method of obstruct laminated film according to claim 1, is characterized in that, comprise the following steps:
S10, polysulfones, organic solvent to be mixed in a heated condition with curing agent, obtain homodisperse counterdie solution; Then the striking on glass of counterdie solution is formed primary membrane, after solidifying, obtain polysulfones counterdie;
S20, cellulose is scattered in water, then adds oxidant, be stirred to and obtain transparent dispersion system; Described oxidant is 2,2,6,6-tetramethyl piperidine-nitrogen-oxide;
S30, the polysulfones counterdie of step S10 to be contacted with the transparent dispersion system of step S20, after drying, obtain described obstruct laminated film.
6. preparation method according to claim 5, is characterized in that, in step S10, organic solvent is selected from least one in N-methyl-pyrrolidon, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO); Curing agent is selected from least one in polyethylene glycol, polyvinylpyrrolidone, propane diols.
7. the preparation method according to claim 5 or 6, is characterized in that, in step S10, with the polysulfones of 10 weight portions for benchmark, the consumption of organic solvent is 30 ~ 90 weight portions, and the consumption of curing agent is 1 ~ 5 part of weight portion.
8. preparation method according to claim 5, it is characterized in that, in step S10, the step mixed under described heating condition comprises: polysulfones, organic solvent are first mixed at 70 ~ 80 DEG C with curing agent, be then stirred to the rotating speed of 100 ~ 300r/min and obtain homodisperse solution.
9. the preparation method according to claim 5 or 8, is characterized in that, before being also included in striking film forming, counterdie solution is carried out to the step of deaeration; The step of described deaeration comprises: counterdie solution is left standstill 8 ~ 24h at 50 ~ 60 DEG C.
10. preparation method according to claim 5, is characterized in that, in step S10, the step that striking forms primary membrane comprises: fallen on glass by counterdie solution, scrape make film with scraper, and leaves standstill 1 ~ 6min at room temperature, obtains described primary membrane.
11. preparation methods according to claim 5, is characterized in that, in step S10, described in the step of solidifying comprise: primary membrane is put into frozen water together with bulk glass and soaks 6 ~ 10min, then soak through room temperature washing, finally dry 2 ~ 4h at 50 ~ 70 DEG C.
12. preparation methods according to claim 5, is characterized in that, in step S20, with the cellulose of 10 weight portions for benchmark, the consumption of water is 10 ~ 40 weight portions, and the consumption of oxidant is 1 ~ 3 weight portion.
13. preparation methods according to claim 5, it is characterized in that, in step S30, be: by polysulfones counterdie mass-impregnation in transparent dispersion system after drying, obtain the polysulfones counterdie that upper and lower two surfaces all have cellulose layer by the step that polysulfones counterdie contacts with transparent dispersion system.
14. preparation methods according to claim 13, is characterized in that, dip time is 6 ~ 15min.
15. preparation methods according to claim 5 or 13, is characterized in that, in step S30, dry condition comprises: temperature is 60 ~ 90 DEG C, and the time is 20 ~ 40min.
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| CN114127363A (en) * | 2019-02-22 | 2022-03-01 | 吉慕莎有限公司 | Recyclable composites, especially for food packaging |
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| US20110159303A1 (en) * | 2008-03-12 | 2011-06-30 | Shin-Etsu Chemical Co., Ltd. | Sintered silicon oxide for film vapor deposition, its production method, and method for producing silicon oxide vapor deposition film |
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| JP2002348522A (en) * | 2001-05-29 | 2002-12-04 | Toppan Printing Co Ltd | Coating agent and laminated material using the same |
| CN1542053A (en) * | 2003-11-05 | 2004-11-03 | 四川大学 | Polysulfone porous microsphere and membrane, preparation method and application thereof |
| US20110159303A1 (en) * | 2008-03-12 | 2011-06-30 | Shin-Etsu Chemical Co., Ltd. | Sintered silicon oxide for film vapor deposition, its production method, and method for producing silicon oxide vapor deposition film |
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