CN107033371B - A kind of preparation method of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite hydrogel - Google Patents
A kind of preparation method of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite hydrogel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 7
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 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
- 239000000725 suspension Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Chemical group 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000004224 protection Effects 0.000 abstract description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 238000010413 gardening Methods 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010257 thawing Methods 0.000 abstract description 2
- 229920005615 natural polymer Polymers 0.000 abstract 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 69
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- -1 CNC Compound Chemical class 0.000 description 5
- 239000000499 gel Substances 0.000 description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012549 training Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
Abstract
A kind of preparation method of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite hydrogel, belongs to polymeric material field and photosensitive material field.The present invention includes: that natural polymer CNC is added in PVA solution, obtains PVA/CNC mixed solution.Again by the N containing carbon-carbon double bond and amino, N '-methylene-bisacrylamide (MBA) is added in mixed solution, MBA and PVA, hydrogen bond action occurs for CNC, it polymerize under ultraviolet light simultaneously, it is handled finally by circulating frozen defrosting, obtains photo-crosslinking PVA/CNC composite hydrogel.This photo-crosslinking PVA/CNC composite hydrogel improves the mechanical property of PVA hydrogel, so that it has better utilization in multiple fields such as agricultural gardening, biological medicine, environmental protections.
Description
Technical field
The present invention relates to a kind of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite hydrogel preparation method,
Photocrosslinking agent is especially added and obtains the light curing compound material of activeness and quietness, belongs to field of polymer composite material.
Background technique
Hydrogel is widely used in agricultural gardening, biological medicine, environment as a kind of high water-keeping material of high water absorption, hydrogel
The multiple fields such as protection.But the disadvantages such as traditional hydrogel often has an intensity difference, and toughness is low, prepare high-intensity and high-tenacity
Hydrogel have been a hot spot of research.
Water-soluble poval (PVA) is to hydrolyze to obtain by polyvinyl acetate, and structural formula is-CH2CH(OH)nIt is a kind of band
The high molecular polymer of hydroxyl.Polyvinyl alcohol (PVA) is to prepare hydrogel due to its good biocompatibility and high-hydrophilic
Traditional raw material.However, since PVA has a large amount of soft segment, so pure PVA hydrogel often has lower mechanical property
Energy.PVA hydrogel to be made has good mechanical property, needs to be modified it processing.
Nanocrystalline cellulose (Cellulose Nanocrystals, CNC), or it is called cellulose crystallite, its diameter
For a few to tens of nanometers, length dozens to a few hundred nanometers.The CNC extracted from renewable resource, it has excellent machine
Tool performance (high intensity and modulus), big specific surface area, it is environmental-friendly and inexpensive the advantages that.CNC excellent mechanical performance
And hydrogen bond is formed with the hydroxyl on PVA, the mechanical property of PVA hydrogel can be improved.
Photo-crosslinking technology is as a kind of novel crosslinking technological, and photo-crosslinking technology is using the ultraviolet light of low energy as radiation source.
The advantages that with easy to operate, environmental protection is quick, at low cost.It is double containing carbon carbon in N, N '-methylene-bisacrylamide (MBA) molecule
With the substance rich in hydroxyl hydrogen bond action can occur for key and amino.Under the action of photoinitiator and ultraviolet light, N, N '-sub-
Bisacrylamide can polymerize, and can be used as photocrosslinking agent and apply in all kinds of composite materials.
Summary of the invention
The purpose of the present invention is natural macromolecular CNC is added in PVA, the cost of PVA based composites, enhancing are reduced
The mechanical property of PVA based composites.In addition MBA is added in PVA/CNC composite material, contains carbon-carbon double bond in MBA molecule
And amino, hydrogen bond action can occur with the hydroxyl on PVA, while can polymerize under ultraviolet light, further mention
The mechanical property of high PVA/CNC composite material.
The purpose of the present invention is be achieved through the following technical solutions: a kind of photo crosslinked polyethylene alcohol/nanocrystalline cellulose
The preparation method of PVA/CNC composite hydrogel includes following step:
(1) preparation of PVA/CNC mixed solution: CNC is taken to be dissolved in the suspension for preparing into mass fraction 1% in deionized water
Liquid, in 100W supersonic wave cleaning machine, ultrasonic disperse 30min.It is again 1:0.05~1:0 by the mass ratio of PVA and CNC, by CNC
Suspension is added in PVA solution, and 90 DEG C of stirring 2h of constant temperature obtain PVA/CNC mixed solution.
(2) above-mentioned steps (1) PVA/CNC mixed solution the preparation of photo-crosslinking PVA/CNC mixed solution: is cooled to 60
DEG C, photocrosslinking agent and photoinitiator is added, 1h is stirred in shading, is poured into culture dish after standing defoaming, exposes one under ultraviolet light
The section time, obtain photo-crosslinking PVA/CNC mixed solution.
(3) preparation of photo-crosslinking PVA/CNC composite hydrogel: above-mentioned steps (2) photo-crosslinking PVA/CNC mixed solution is close
Envelope, is put into refrigerator, freezes 20h at -20 DEG C, place into the 4h that thaws at room temperature.Circulating frozen thaws 5~7 times.Obtain light friendship
Join PVA/CNC composite hydrogel.
PVA and CNC mass ratio described in step (1) is 1:0.05~1:0.
Photocrosslinking agent described in step (2) is selected from N, N '-methylene-bisacrylamide, acrylic acid, acrylamide, clothing health
Acid, hydroxy-ethyl acrylate, dosage are the 1%~10% of PVA mass.
Photoinitiator described in step (2) is water-soluble light trigger.Dosage is the 1%~10% of PVA mass.
Cryogenic temperature described in step (3) is -20 DEG C.
Circulating frozen defrosting number described in step (3) is 5~7 times.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that PVA strand contain great amount of hydroxy group (-
OH), good water solubility is made it have, it can be close to connect with the natural macromolecular containing hydroxyl by hydrogen bond crosslinks.Again plus
Enter colorless and transparent, the MBA of hypotoxicity obtains the photo-crosslinking PVA/CNC composite hydrogel of dual network structure as photocrosslinking agent,
Photo-crosslinking PVA/CNC composite hydrogel possesses more outstanding mechanical property, so that it is in agricultural gardening, biological medicine, environment
The multiple fields such as protection have better utilization.
Detailed description of the invention:
Fig. 1 is photo-crosslinking PVA/CNC composite hydrogel and non-photo-crosslinking PVA/CNC Compound Water prepared in embodiment 1
Gel, the tensile stress strain diagram of pure PVA hydrogel.
Fig. 2 is photo-crosslinking PVA/CNC composite hydrogel and non-photo-crosslinking PVA/CNC Compound Water prepared in embodiment 1
Gel, compressive strength figure of the pure PVA hydrogel under 98% compressive deformation.
Specific embodiment
In order to better explain the present invention, the present invention is further explained in detail combined with specific embodiments below, but this hair
Bright embodiment is without being limited thereto.
Embodiment 1
(1) preparation of PVA/CNC mixed solution: CNC is taken to be dissolved in the suspension for preparing into mass fraction 1% in deionized water
Liquid, in 100W supersonic wave cleaning machine, ultrasonic disperse 30min.Take 3g PVA and 34.5mL deionized water in three-necked flask,
2h is stirred at 90 DEG C, after being completely dissolved, 0.02gCNC is added, continues to stir, obtains PVA/CNC mixed solution.
(2) above-mentioned steps (1) PVA/CNC mixed solution the preparation of photo-crosslinking PVA/CNC mixed solution: is cooled to 60
DEG C, 60 DEG C are cooled to, is added 0.15g photocrosslinking agent MBA (N, N '-methylene-bisacrylamide), after being stirred until homogeneous, is added
1h is stirred in (2- hydroxyl -4- (2- the hydroxy ethoxy) -2- methylbenzene) shading of 0.09g photoinitiator 2959, pours into training after standing defoaming
It supports in ware, under the ultraviolet lamp (Fusion UV systems.USA) of a F300, with 2cm/min transmission 6 times, obtains light friendship
Join PVA/CNC mixed solution.
(3) preparation of photo-crosslinking PVA/CNC composite hydrogel: above-mentioned steps (2) photo-crosslinking PVA/CNC mixed solution is close
Envelope, is put into refrigerator, freezes 20h at -20 DEG C, place into the 4h that thaws at room temperature.Circulating frozen thaws 5 times.Obtain photo-crosslinking
PVA/CNC composite hydrogel.
Embodiment 2
(1) preparation of PVA/CNC mixed solution: CNC is taken to be dissolved in the suspension for preparing into mass fraction 1% in deionized water
Liquid, in 100W supersonic wave cleaning machine, ultrasonic disperse 30min.Take 3g PVA and 34.5mL deionized water in three-necked flask,
2h is stirred at 90 DEG C, after being completely dissolved, 0.03gCNC is added, continues to stir, obtains PVA/CNC mixed solution.
(2) above-mentioned steps (1) PVA/CNC mixed solution the preparation of photo-crosslinking PVA/CNC mixed solution: is cooled to 60
DEG C, 60 DEG C are cooled to, is added 0.30g photocrosslinking agent MBA (N, N '-methylene-bisacrylamide), after being stirred until homogeneous, is added
1h is stirred in (2- hydroxyl -4- (2- the hydroxy ethoxy) -2- methylbenzene) shading of 0.15g photoinitiator 2959, pours into training after standing defoaming
It supports in ware, irradiates 300s under the ultraviolet point light source of UV-1000IWATA, obtain photo-crosslinking PVA/CNC mixed solution.
(3) preparation of photo-crosslinking PVA/CNC composite hydrogel: above-mentioned steps (2) photo-crosslinking PVA/CNC mixed solution is close
Envelope, is put into refrigerator, freezes 20h at -20 DEG C, place into the 4h that thaws at room temperature.Circulating frozen thaws 7 times.Obtain photo-crosslinking
PVA/CNC composite hydrogel.
By photo-crosslinking PVA/CNC composite hydrogel and non-photo-crosslinking PVA/CNC compound water congealing prepared in embodiment 1
Glue, it is long l=15 ± 2mm, wide b=4.0 ± 0.2mm, the dumbbell shape of thick h=2.0 ± 1mm that pure PVA hydrogel, which cuts out sample into specification,
Batten sample preparation dumbbell shape batten is tested with KDIII-5 type microcomputer controlled electronic universal tester, obtains stretching as shown in Figure 1
Stress strain diagram.The PVA/CNC water-setting of non-photo-crosslinking it will be seen from figure 1 that the PVA/CNC composite hydrogel of photo-crosslinking compares
Glue, pure PVA hydrogel have higher tensile strength and elongation at break, this may be since the PVA/CNC of photo-crosslinking is compound
Hydrogel has more stable network structure, so that it possesses higher tensile strength and elongation at break.
By photo-crosslinking PVA/CNC composite hydrogel and non-photo-crosslinking PVA/CNC composite hydrogel prepared in embodiment 1
According to 7~10mm of diameter, the specification of high 7~10mm is tailored into cylindrical sample.With the omnipotent examination of KDIII-5 type microcomputer controlled electronic
It tests machine and carries out compression experiment.Figure it is seen that PVA/CNC water of the PVA/CNC composite hydrogel of photo-crosslinking than non-photo-crosslinking
Gel and pure PVA hydrogel have higher compressive strength in 98% compression strain, this may be the PVA/ due to photo-crosslinking
CNC composite hydrogel has more stable network structure, and certain supporting role is played to hydrogel, possesses it higher
Compressive strength.
Claims (2)
1. a kind of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite hydrogel preparation method:
(1) preparation of PVA/CNC mixed solution: taking CNC to be dissolved in the suspension for preparing into mass fraction 1% in deionized water,
In 100W supersonic wave cleaning machine, ultrasonic disperse 30min, then pressing the mass ratio of PVA and CNC is 1:0.05~1:0, and CNC is suspended
Liquid is added in PVA solution, and 90 DEG C of stirring 2h of constant temperature obtain PVA/CNC mixed solution；
(2) preparation of photo-crosslinking PVA/CNC mixed solution: above-mentioned steps (1) PVA/CNC mixed solution is cooled to 60 DEG C, is added
Enter photocrosslinking agent N, N '-methylene-bisacrylamide MBA and photoinitiator, 1h is stirred in shading, pours into culture dish after standing defoaming
In, under ultraviolet light exposure a period of time, obtain photo-crosslinking PVA/CNC mixed solution；
(3) preparation of photo-crosslinking PVA/CNC composite hydrogel: above-mentioned steps (2) photo-crosslinking PVA/CNC mixed solution is sealed,
It is put into refrigerator, freezes 20h at -20 DEG C, place into the 4h that thaws at room temperature, circulating frozen thaws 5~7 times, obtains photo-crosslinking
PVA/CNC composite hydrogel.
2. a kind of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite hydrogel preparation according to claim 1
Method, it is characterised in that photoinitiator described in step (2) be water-soluble light trigger, dosage be PVA mass 1%~
10%.
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| KR20190039639A (en) * | 2017-10-05 | 2019-04-15 | 메르크 파텐트 게엠베하 | Compositions comprising functionalized polyvinyl alcohol and nanocapsules containing a liquid-crystalline medium |
| CN109206666A (en) * | 2018-04-27 | 2019-01-15 | 张金荣 | A kind of nanocrystal cellulose aquagel and preparation method thereof |
| CN108888803A (en) * | 2018-07-11 | 2018-11-27 | 蒋青 | A kind of biological support and preparation method thereof, purposes and aquogel system |
| CN109266252B (en) * | 2018-09-14 | 2019-09-03 | 江南大学 | A kind of photo-crosslinking PVA-SbQ/CNC/DA compound water congealing glue adhesive agent and preparation method thereof |
| CN109749097B (en) * | 2019-01-17 | 2022-04-26 | 中南林业科技大学 | Preparation method of environment-friendly rapid self-repairing hydrogel |
| CN112387222B (en) * | 2020-10-28 | 2022-04-19 | 中国工程物理研究院激光聚变研究中心 | Preparation method of Co-Ni bimetallic aerogel |
| CN113376914B (en) * | 2021-05-31 | 2022-11-04 | 西南医科大学 | Stretchable microcapsule film for reflective display and preparation method thereof |
| CN113321770B (en) * | 2021-06-22 | 2022-07-01 | 江南大学 | Preparation method of temperature-sensitive hydrogel |
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