CN102604134B - Cellulose based water-absorbing and oil-absorbing film and preparation method thereof - Google Patents
Cellulose based water-absorbing and oil-absorbing film and preparation method thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 32
- 239000001913 cellulose Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000004159 Potassium persulphate Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- -1 washing Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000011358 absorbing material Substances 0.000 abstract 1
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 33
- 235000019198 oils Nutrition 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000002745 absorbent Effects 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a preparation method of a cellulose based water-absorbing and oil-absorbing film. According to the invention, water-absorbing substances and oil-absorbing substances are grafted on lignocellulose, the prepared film is smart and convenient to use and is wide in application fields. The homogeneous grafting copolymerization is adopted, and the problems of the microphase separation of heterogeneous copolymerization, unsatisfactory grafting effect and uneven component distribution are avoided effectively. As the substrate material (namely, cellulose) has good degradability and can eliminate the pollution of the waste synthesized material to the environment and maintains the ecological balance, the problem that the common water-absorbing and oil-absorbing materials can not meet the water absorbing and oil absorbing properties and biodegradation simultaneously can be solved.
Description
Technical field
The present invention relates to a kind of cellulose base water suction oil suction film, belong to the natural macromolecular material field.
Background technology
Mierocrystalline cellulose is the maximum natural high polymer of quantity on the earth, comes from trees, straw, cotton and other agricultural byproducts, and its cost is low, belongs to renewable resources.The derivatize product of Mierocrystalline cellulose after by the physics and chemistry modification has been widely used in the fields such as chemical industry, medicine, environmental protection, material of construction, petroleum chemistry, therefore Mierocrystalline cellulose, as a kind of eco-friendly renewable resources, makes countries in the world all attach great importance to the research and development to it.Traditional fibre grafting copolyreaction is all carried out in nonhomogeneous system, if these reactions are carried out in homogeneous system, just can effectively control the substitution value of derivatived cellulose, regularly substituted radical is incorporated on cellulosic backbone, control better the physicochemical property of products obtained therefrom than heterogeneous conditions, be conducive to improve the homogeneity of speed of response and product property, improve its range of application.Therefore, adopt the homogeneous phase method to carry out graft polymerization reaction, there is more importantly social benefit.
Amphipathic graft copolymer (being called for short AGP) is one of focus of current functional high molecule material research field.Amphipathic wetting ability and the lipophilicity of referring to, be that inconsistent two kinds of chains on thermodynamics are connected together by chemical bond-linking, thereby realized the assembling of amphiphilic species at molecular level.Amphipathic nature polyalcohol can be divided into graft copolymer and segmented copolymer structure.Yet the double suction multipolymer is different from amphipathic multipolymer, it is not only hydrophilic, oleophylic, the more important thing is that it can absorb water and can oil suction.If this polymkeric substance is put into to the medium of oil/water, stretching, extension in the oil/water two-phase medium, swelling and the absorption respectively of its oleophylic and hydrophilic segment, and be suspended in oil and water interface even.
Traditional take the single water suction oil absorption material that resin is matrix, raw material comes from petroleum chemicals fully, and this class sintetics is degradable through 500 years ability at nature, and environment is caused to very big harm.The Mierocrystalline cellulose that utilizes occurring in nature the most extensively to exist, produce the cellulose base water suction oil absorption material with broad prospect of application, the waste liquor treating agent as administering in industry and daily life of usining is administered environment, the comprehensive production cost decrease of oil suction product not only can make to absorb water, and due to the tiny internal structure of Mierocrystalline cellulose, the absorbent of the oil absorption material that can make to absorb water be improved significantly.Simultaneously, due to the excellent degradability of cellulose materials itself, also can eliminate the pollution of discarded synthetic imbibition agent to environment, maintaining ecological balance.Therefore, research environment close friend's reproducible cellulose base water suction oil absorption material, not only can reduce the destruction to environment, the waste of the energy, and the oil absorption material production cost decrease that can also make to absorb water, this also has great importance to enlarging its Application Areas.
The people such as Zhang Mingjie are at New Chemical Materials, have reported that starch graft acrylamide and methyl methacrylate prepare the method for the oil-absorbing resin that absorbs water in 35 (1), 59～60,2007.The water absorbent rate of the starch base water suction oil-absorbing resin that this method makes is 8-12g/g, and the oil suction multiplying power is 4-7g/g.It adopts heterogeneous polymerization, makes product water suction oil suction multiplying power not high, lacks society and economic benefit.
The people such as Cao Aili are in fine chemistry industry, have reported a kind of method for preparing the oil-absorbing resin that absorbs water by dispersion method in 21 (1), 90～94,2004.The employing polyvinylpyrrolidone is dispersion agent, and vinylbenzene and methacrylic acid are comonomer, and Diisopropyl azodicarboxylate is initiator, and divinylbenzene is linking agent, and synthesizing water absorbent rate is that 4.2g/g, oil suction multiplying power are 7.2g/g, has the polymers of double suction function.Equally, its water suction oil suction effect is not ideal enough, and the product feature of environmental protection is lower, lacks economic and practical.Therefore, need to find the preparation method of a kind of more environmental friendliness and economical and practical water suction oil absorption material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cellulose base water suction oil suction film, comprise the steps:
1. the ethylenediamine solution that is 75% by lignocellulose with mass concentration is 1: 15～20 to mix in mass ratio, under 40 ℃, stirs 4h, filters, and washing is to neutral, and squeezing, obtain lignocellulose I; Wherein, the polymerization degree of described lignocellulose is 400～1500;
2. the lignocellulose I 1. step obtained and alkaline substance solution are 100: 3～6 to mix in mass ratio, and under-10～-20 ℃, after freezing 1～5h, stirring at room, obtain evenly, transparent mixed liquor I; Wherein, the mixture that described alkaline matter is sodium hydroxide and urea or thiocarbamide;
3. under protection of inert gas, in mixed liquor I, add initiator, under 30～60 ℃, stir 0.5～1h; Wherein, the mass ratio of described initiator and lignocellulose is 0.01～0.06: 1;
4. add the monomer of 1～4 times of lignocellulose quality, under 40～70 ℃, stir 1～6h, add N,N methylene bis acrylamide, continue to stir 1～3h, obtain mixed liquor I I; Wherein, described monomer is acrylamide and butyl methacrylate, and the mass ratio of described N,N methylene bis acrylamide and lignocellulose is 0.005～0.04: 1;
5. mixed liquor I I is centrifugal, knifing, be placed on the H of 10wt%
2SO
4Na with 12wt%
2SO
4Solidify 30min in mixed aqueous solution, washing, ethanol are washed, and dry, and obtain cellulose base water suction oil suction film.
In above-mentioned preparation method, for the optimisation technique scheme, the lignocellulose pre-treatment is block.In alkaline substance solution, the add-on of sodium hydroxide is preferably 5～10% of alkaline substance solution quality, and the add-on of urea or thiocarbamide is preferably 4～12% of alkaline substance solution quality.
In above-mentioned preparation method, initiator is preferably Potassium Persulphate, ammonium persulphate or benzoyl peroxide; Potassium Persulphate most preferably.
In above-mentioned preparation method, better in order to make graft effect, in monomer, the preferred mass ratio of acrylamide and butyl methacrylate is 0.25～4: 1.
In above-mentioned reaction, for further optimization, centrifugal to be preferably at rotating speed be 4000～8000r/min, and the time is to carry out under 15～30min.
The cellulose base water suction oil suction film that provides above-mentioned arbitrary described method to prepare is provided.
Therefore, the present invention has the following advantages:
1, the present invention has realized the homogeneous phase graft copolymerization of Mierocrystalline cellulose and acrylamide and butyl methacrylate, has effectively avoided the heterogeneous polymerization micron-scale phase separation, and graft effect is undesirable, component problem pockety.
2, in the present invention because the body material Mierocrystalline cellulose itself has good degradability, can eliminate the pollution of discarded synthetic materials to environment, maintaining ecological balance, thus met the demand that general water suction oil absorption material can not solve water suction oil absorbency and biological degradation problem simultaneously.
3, raw material sources of the present invention are extensive, and polymerization single polymerization monomer is easy to get and is inexpensive, and reaction process is simple, comprehensive production cost decrease.
4, solvent system of the present invention is than the more environmental protection of existing copper ammon solution, ionic liquid, and cost is lower, more is conducive to realize suitability for industrialized production, has important society and economic benefit.
5, the prepared product of the present invention is function film, and it is lightly convenient to use, and makes Application Areas more extensive.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Investigate the performance of cellulose base water suction oil suction film in the present invention by measuring water absorbent rate and oil suction multiplying power, the performance of larger its film of numerical value of water absorbent rate and oil suction multiplying power is better.
1, water absorbent rate is measured:
Water absorbent rate (Q
1, g/g): accurately take a certain amount of function film (m
1, g) be placed in a certain amount of deionized water, at room temperature, after the abundant imbibition of standing 24h, through 200 purpose copper mesh, filter, (m weighs
2, g), calculate the product water absorbent rate;
Calculating formula is: Q
1=(m
2-m
1)/m
1
2, oil suction multiplying power is measured:
Oil suction multiplying power (Q
2, g/g): accurately take a certain amount of polymerisate (m
3, g) be placed in a certain amount of soybean oil, at room temperature, after the abundant imbibition of standing 24h, through 200 purpose copper mesh, filter, (m weighs
4, g), calculate the product water absorbent rate.
Calculating formula is: Q
2=(m
4-m
3)/m
3
Embodiment 1
1. the Mierocrystalline cellulose 5.0g that is 548 by the polymerization degree is ground into bulk, is placed in the there-necked flask of 250ml, under 40 ℃, adds the ethylenediamine solution that the 100g massfraction is 75%, stirring reaction 4h, and suction filtration, distilled water wash, to neutral, squeezes stand-by;
The alkaline substance solution of the sodium hydroxide that 2. adds 100g to contain 5wt% and the urea of 8wt%, under-12 ℃, freezing 5h, stirring at room, obtain even, transparent mixed liquor I;
3. the Potassium Persulphate that adds 0.24g, stirring reaction 0.5h;
4. the butyl methacrylate that adds acrylamide and the 2.5g of 2.5g, be warming up to 70 ℃ under stirring, isothermal reaction 2h, add the 0.08g N,N methylene bis acrylamide, continues stirring reaction 1h, obtains mixed liquor I I;
5. by mixed liquor I I on whizzer with after deaeration 20min under the rotating speed of 5000r/min, curtain coating knifing on sheet glass, then film being placed in to massfraction is 10wt%H
2SO
4And 12wt%Na
2SO
4Mixed aqueous solution in solidify 30min, through washing, ethanol is washed, and dries, and obtains cellulose base water suction oil suction film.
The water suction oil suction test result of cellulose base water suction oil suction film:
Specimen liquid absorbency rate (Q, g/g)
Water 23.51
Soybean oil 11.55.
Embodiment 2
1. the Mierocrystalline cellulose 4.0g that is 655 by the polymerization degree is ground into bulk, is placed in the there-necked flask of 250ml, under 40 ℃, adds the ethylenediamine solution stirring reaction 4h that the 80g massfraction is 75%, suction filtration, and water washing, to neutral, is squeezed stand-by;
In the alkaline substance solution of the urea that 2. adds 100g to contain 7wt% sodium hydroxide and 12wt%, under-12 ℃, freezing 5 hours, stirring at room, obtained even, transparent mixed liquor I;
3. the Potassium Persulphate that adds 0.18g, stirring reaction 0.5h;
4. the butyl methacrylate that adds acrylamide and the 1.5g of 2.5g, be warming up to 60 ℃ under stirring, isothermal reaction 2h, add the 0.06g N,N methylene bis acrylamide, continues stirring reaction 1h, obtains mixed liquor I I;
5. by mixed liquor I I on whizzer with after deaeration 15min under the rotating speed of 5000r/min, curtain coating knifing on sheet glass, then film being placed in to massfraction is 10wt%H
2SO
4And 12wt%Na
2SO
4Mixed aqueous solution in solidify 30min, through washing, ethanol is washed, and dries, and obtains cellulose base water suction oil suction film.
The water suction oil suction test result of cellulose base water suction oil suction film:
Specimen liquid absorbency rate (Q, g/g)
Water 21.83
Soybean oil 10.21.
Claims (5)
1. the preparation method of a cellulose base water suction oil suction film, comprise the steps:
1. the ethylenediamine solution that is 75% by lignocellulose with mass concentration mixes for 1:15～20 in mass ratio, under 40 ℃, stirs 4h, filters, and washing is to neutral, and squeezing, obtain the lignocellulose I; Wherein, the polymerization degree of described lignocellulose is 400～1500;
2. the lignocellulose I 1. step obtained is mixed for 100:3～6 in mass ratio with alkaline substance solution, and under-10～-20 ℃, after freezing 1～5h, stirring at room, obtain evenly, transparent mixed solution I; Wherein, the mixture that described alkaline matter is sodium hydroxide and urea or thiocarbamide,
Wherein, the add-on of sodium hydroxide is 5～10% of alkaline substance solution quality, and the add-on of urea or thiocarbamide is 4～12% of alkaline substance solution quality;
3. under protection of inert gas, in the mixed solution I, add initiator, under 30～60 ℃, stir 0.5～1h; Wherein, the mass ratio of described initiator and lignocellulose is 0.01～0.06:1;
4. add the monomer of 1～4 times of lignocellulose quality, under 40～70 ℃, stir 1～6h, add N, N '-methylene-bisacrylamide, continue to stir 1～3h, obtains the mixed solution II; Wherein, described monomer is acrylamide and butyl methacrylate, described N, and the mass ratio of N '-methylene-bisacrylamide and lignocellulose is 0.005～0.04:1,
Wherein, the mass ratio of acrylamide and butyl methacrylate is 0.25～4:1;
5. the mixed solution II is centrifugal, knifing, be placed on the H of 10wt%
2SO
4Na with 12wt%
2SO
4Solidify 30min in mixed aqueous solution, washing, ethanol are washed, and dry, and obtain cellulose base water suction oil suction film.
2. the preparation method of cellulose base water suction oil suction film according to claim 1, is characterized in that the initiator during described step 3. is selected from Potassium Persulphate, ammonium persulphate and benzoyl peroxide.
3. the preparation method of cellulose base water suction oil suction film according to claim 2, is characterized in that the initiator during described step 3. is Potassium Persulphate.
4. according to the preparation method of the described cellulose base of claim 1 or 3 water suction oil suction film, it is characterized in that centrifugal during described step is 5. is to be 4000～8000r/min at rotating speed, the time is to carry out under 15～30min.
5. the cellulose base water suction oil suction film that method claimed in claim 1 prepares.
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| CN105131187A (en) * | 2015-10-09 | 2015-12-09 | 厦门大学 | Modified regenerated cellulose membrane and preparation method and application thereof |
| CN111304949A (en) * | 2020-03-02 | 2020-06-19 | 赛尔睿思复合新材料科技(苏州)有限公司 | Water-absorbing and oil-absorbing paper-like material and preparation method thereof |
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